Low crystallinity glass-ceramics

ABSTRACT

Embodiments of the present disclosure pertain to crystallizable glasses and glass-ceramics that exhibit a black color and are opaque. In one or more embodiments, the crystallizable glasses and glass-ceramics include a precursor glass composition that exhibits a liquidus viscosity of greater than about 20 kPa*s. The glass-ceramics exhibit less than about 20 wt % of one or more crystalline phases, which can include a plurality of crystallites in the Fe2O3—TiO2—MgO system and an area fraction of less than about 15%. Exemplary compositions used in the crystallizable glasses and glass-ceramics include, in mol %, SiO2 in the range from about 50 to about 76, Al2O3 in the range from about 4 to about 25, P2O5+B2O3 in the range from about 0 to about 14, R2O in the range from about 2 to about 20, one or more nucleating agents in the range from about 0 to about 5, and RO in the range from about 0 to about 20.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No. 15/880,030filed on Jan. 25, 2018, which is a continuation of U.S. application Ser.No. 14/623,674 filed on Feb. 17, 2015, which claims the benefit ofpriority under 35 U.S.C. § 119 of U.S. Provisional Application Ser. No.61/942,749 filed on Feb. 21, 2014 the content of which is relied uponand incorporated herein by reference in its entirety.

BACKGROUND

Aspects of this disclosure generally relate crystallizable glasses andglass-ceramics and processes for forming such crystallizable glasses andglass-ceramics. Specific aspects relate to crystallizable glassesexhibiting high liquidus viscosity and glass-ceramics exhibiting lowcrystallinity, which can be chemically strengthened.

Consumer electronic devices such as notebook computers, personal digitalassistants (PDAs), portable navigation device (PNDs), media players,mobile phones, portable inventory devices (PIDs), etc. (frequentlyreferred to as “portable computing devices”) have converged while at thesame time becoming small, light, and functionally more powerful. Onefactor contributing to the development and availability of such smallerdevices is an ability to increase computational density and operatingspeed by ever decreasing electronic component sizes. However, the trendto smaller, lighter, and functionally more powerful electronic devicespresents a continuing challenge regarding design of some components ofthe portable computing devices.

Components associated with the portable computing devices encounteringparticular design challenges include the enclosure or housing used tohouse the various internal/electronic components. This design challengegenerally arises from two conflicting design goals—the desirability ofmaking the enclosure or housing lighter and thinner, and thedesirability of making the enclosure or housing stronger and more rigid.Lighter enclosures or housings, typically thin plastic structures withfew fasteners, tend to be more flexible while having a tendency tobuckle and bow as opposed to stronger and more rigid enclosure orhousings, typically thicker plastic structures with more fastenershaving more weight. Unfortunately, plastics are soft materials that areeasily scratched and scuffed degrading their appearance.

Among known classes of materials are glass-ceramics that are used widelyin various other applications and are much harder and more scratchresistant than polymers. Glass-ceramics are used widely in appliances(e.g., cooktops, ovens, dishwashers and refrigerators), cookware, andeating utensils, such as bowls, dinner plates, and the like. Transparentglass-ceramics are used in the production of oven and/or furnacewindows, optical elements, mirror substrates, and the like.Glass-ceramics are typically made by thermally treating crystallizableglass compositions at pre-specified temperatures for pre-specifiedperiods of time to nucleate and grow crystalline phases in a glassmatrix. Two glass-ceramics based on the SiO₂—Al₂O₃—Li₂O glass systemcomprise those having either β-quartz solid solution (β-quartz ss) asthe predominant crystalline phase or β-spodumene solid solution(β-spodumene ss) as the predominant crystalline phase. Theseglass-ceramics are typically not formable by fusion forming techniquesand, thus, have that forming limitation.

There exists a need for glass and glass-ceramic materials andtechnologies that provide improved choices for enclosures or housings ofportable computing devices and for use in appliances.

SUMMARY

A first aspect of the present disclosure pertains to a glass-ceramichaving a low crystallinity. In one or more embodiments, theglass-ceramic includes less than about 20 wt % of one or morecrystalline phases. In one option, the one or more crystalline phasesmay include a solid solution of MgO, TiO₂, and Fe₂O₃. In another option,the one or more crystalline phases may include a plurality ofcrystallites in the Fe₂O₃—TiO₂—MgO system. In one or more examples, thecrystallites may include MgO, Fe₂O₃, TiO₂, or combinations thereof. Thecrystallites may include MgO in an amount in the range from about 5 mol% to about 50 mol %, Fe₂O₃ in an amount in the range from about 15 mol %to about 65 mol %, and/or TiO₂ in an amount in the range from about 25mol % to about 45 mol %. In some embodiments, the glass-ceramics caninclude TiO₂ and a ratio of TiO₂:Fe₂O₃ in the range from about 0.1 toabout 3. In other embodiments, the glass-ceramics can include TiO₂ and aratio of TiO₂:Fe₂O₃ of greater than about 2. In one example, theplurality of crystallites may include at least one of magnetite,pseudobrookite, and ε-Fe₂O₃. In one or more embodiments, the pluralityof crystallites forms an area fraction of about 15% or less or about 10%or less.

In some embodiments, the glass-ceramic includes one or more ε-Fe₂O₃crystallites. In some cases, the ε-Fe₂O₃ crystallites can include Mg2+,Fe2+ ions or a combination of Mg2+ and Fe2+ ions. In other embodiments,the one or more crystalline phases present the glass-ceramics caninclude a solid solution of ε-Fe₂O₃ and MgTiO₃.

The glass-ceramics according to one or more embodiments may exhibit ablack and opaque color. In one or more embodiments, the glass-ceramicsmay exhibit a color presented in CIELAB color space coordinates for CIEilluminant D65 determined from reflectance spectra measurements using aspectrophotometer with SCE of the following ranges: L*=from about 14 toabout 30, a*=from about −1 to about +3, and b*=from about −7 to about+3.

The glass-ceramic of one or more embodiments includes a precursor glassexhibiting a liquidus viscosity of greater than about 20 kPa*s or about50 kPa*s or greater. In some embodiments, the precursor glass issubstantially transparent and exhibits an average transmission of atleast about 10% in the visible-to-near-IR spectrum in the wavelengthrange from about 375 nm to about 1000 nm. The composition of theglass-ceramics and/or precursor glass may include, in mol %: SiO₂ in therange from about 50 to about 76, Al₂O₃ in the range from about 4 toabout 25, P₂O₅+B₂O₃ in the range from about 0 to about 14, R₂O in therange from about 2 to about 20, one or more nucleating agents in therange from about 0 to about 5, and RO in the range from about 0 to about20. Exemplary nucleating agents include TiO₂. The composition of theglass-ceramics and/or precursor glass can also include Fe₂O₃, on anoxide basis, in mol %, in an amount in the range from about 0 to about5.

Another exemplary glass-ceramic and/or precursor glass composition mayinclude, on an oxide basis, in mol %: SiO₂ in an amount in the rangefrom about 58 to about 72, Al₂O₃ in an amount in the range from about 8to about 20, B₂O₃ in an amount in the range from about 0 to about 12,R₂O in an amount in the range from about 0 to about 20, RO in an amountin the range from about 0 to about 10, SnO₂ in an amount in the rangefrom about 0 to about 0.5, TiO₂ in an amount in the range from about0.25 to about 5, and Fe₂O₃ in an amount in the range from about 0.25 toabout 5. The composition may optionally include one or more of thefollowing compositional relationships: R₂O—Al₂O₃ in the range from about−2 to about 3; and R_(x)O—Al₂O₃ in the range from about −2 to about 5.

Yet another exemplary glass-ceramic and/or precursor glass compositionmay include, on an oxide basis, in mol %: SiO₂ in an amount in the rangefrom about 62 to about 68, Al₂O₃ in an amount in the range from about 10to about 14, B₂O₃ in an amount in the range from about 3 to about 10,Li₂O in an amount in the range from about 0 to about 5, Na₂O in anamount in the range from about 5 to about 18, MgO in an amount in therange from about 1 to about 3, CaO in an amount in the range from about0 to about 2, SnO₂ in an amount in the range from about 0 to about 0.2,TiO₂ in an amount in the range from about 0.25 to about 5, and Fe₂O₃ inan amount in the range from about 0.25 to about 5. The composition mayoptionally include one or more of the following compositionalrelationships: R₂O—Al₂O₃ in the range from about −1 to about 1.5; andR_(x)O—Al₂O₃ in the range from about 0 to about 2.5.

The glass-ceramics described herein also exhibit improved mechanicalproperties. In one or more embodiments, the glass-ceramic may bechemically strengthened (e.g., by ion exchange process(es)). Suchglass-ceramics may exhibit a compressive stress of at least about 200MPa and a depth of compressive stress layer of at least about 15 μm. Inone or more embodiments, the glass ceramics exhibit an average edgestrength, as measured by 4—point bend of at least about 700 MPa. Inother embodiments, the glass-ceramics exhibit an average flexuralstrength, as measured by ring-on-ring testing, of about 2000 N orgreater. In yet other embodiments, the glass-ceramics exhibit an averageflexural strength, as measured by abraded ring-on-ring testing, of about1000 N or greater.

Numerous other aspects of embodiments, embodiments, features, andadvantages of this disclosure will appear from the following descriptionand the accompanying drawings. In the description and/or theaccompanying drawings, reference is made to exemplary aspects and/orembodiments of this disclosure which can be applied individually orcombined in any way with each other. Such aspects of embodiments and/orembodiments do not represent the full scope of this disclosure.Reference should therefore be made to the claims herein for interpretingthe full scope of this disclosure. In the interest of brevity andconciseness, any ranges of values set forth in this specificationcontemplate all values within the range and are to be construed assupport for claims reciting any sub-ranges having endpoints which arereal number values within the specified range in question. By way of ahypothetical illustrative example, a recitation in this disclosure of arange of from about 1 to 5 shall be considered to support claims to anyof the following ranges: 1-5; 1-4; 1-3; 1-2; 2-5; 2-4; 2-3; 3-5; 3-4;and 4-5. Also in the interest of brevity and conciseness, it is to beunderstood that such terms as “is,” “are,” “includes,” “having,”“comprises,” and the like are words of convenience and are not to beconstrued as limiting terms and yet may encompass the terms “comprises,”“consists essentially of,” “consists of,” and the like as isappropriate.

These and other aspects, advantages, and salient features of thisdisclosure will become apparent from the following description, theaccompanying drawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings referenced herein form a part of the specification.Features shown in the drawings are meant to be illustrative of some, butnot all, embodiments of this disclosure, unless otherwise explicitlyindicated, and implications to the contrary are otherwise not to bemade.

FIG. 1 shows comparisons of the transmission spectra for visible andinfrared (IR) wavelengths obtained for glasses as-made and heat treatedfrom Example Composition 15;

FIG. 2 shows the X-ray diffraction (XRD) pattern obtained for aglass-ceramic made from Example Composition 3 after heat treating at700° C. for 4 hours;

FIG. 3 shows the XRD pattern obtained for a glass-ceramic made fromExample Composition 16 after heat treating at 750° C. for 4 hours,showing the presence of pseudobrookite for which line broadeninganalysis suggests crystallite sizes of roughly between 15-20 nm;

FIG. 4 shows the viscosity versus temperature curve denoting theliquidus temperature and viscosity for a crystallizable glass made fromExample Composition 15;

FIG. 5 shows a schematic illustration of a cross section of an IX,glass-ceramic and associated characterizing parameters: compressivestress (σ_(s)) in the IX, glass-ceramic's surface layer; surfacecompression (CS); central tension (CT); sample thickness (t); and depthof layer (DOL) which is the perpendicular distance from the surface ofthe sample to the location within the sample at which the stresseschanges sign {i.e., zero} resulting from surface compression and centraltension) that can be determined from, for example, the sodium (Na)and/or potassium (K) concentration;

FIG. 6 shows DOL as a function of CS for glass-ceramics made accordingto one or more embodiments;

FIG. 7 shows an XRD pattern of a glass-ceramic made from ExampleComposition 3, after ceramming at 750° C. for 4 hours, an XRD pattern ofa glass-ceramic made from Example Composition 10, after ceramming at750° C. for 4 hours, an XRD pattern of a glass-ceramic made from ExampleComposition 17, after ceramming at 750° C. for 4 hours, and an XRDpattern of a crystallizable glass made from Example Composition 10 afterannealing;

FIG. 8 shows the average dielectric constant and loss tangent as afunction of R₂O—Al₂O₃ for glass-ceramics made from Example Compositions2-7, after ceramming at 750° C. for 4 hours, over the frequency range of400 to 3000 MHz;

FIG. 9 shows the average dielectric constant and loss tangent as afunction of Fe₂O₃ content over the frequency range of 400 to 3000 MHzfor glass-ceramics made from Example Compositions 9, 12 and 13, afterceramming at 700° C. for 4 hours;

FIG. 10 shows the transmission spectra of a crystallizable glass orglass-ceramic, made from Example Composition 9, having thickness ofabout 0.8 mm, after being subjected to various heat treatments;

FIG. 11 shows in situ transmission at various wavelengths during theceramming process of a glass-ceramic made from Example Composition 16through 0.5 mm path length;

FIG. 12 illustrates extinction spectra through 0.8 mm thick samples ofglass-ceramics made from Example Composition 14, after ceramming atvarious temperatures between 700 and 850° C.;

FIG. 13 shows an Fe L23 EELS spectra of a glass-ceramic made fromExample Composition 14, after ceramming at various temperatures, with aninset showing Fe3+/Total Fe ratio as a function of ceram temperature;

FIG. 14A shows a TEM micrograph of a glass-ceramic made from ExampleComposition 16, after ceramming at 750° C. for 4 hours;

FIG. 14B shows elemental intensity maps showing Fe, Ti and Mg enrichmentand Si depletion in the crystallites of the glass-ceramic shown in FIG.14A;

FIG. 15 shows the compositions of crystallites in Example Compositions14 and 18 and in the glass-ceramics made from Example Compositions 14and 18, at various ceram temperatures superimposed on the MgO—TiO₂—Fe₂O₃1000° C. phase diagram;

FIG. 16 is a graph illustrating the change in transmission withdifferent compositions and ceramming temperatures;

FIG. 17 is a graph showing an XRD trace of a glass-ceramic formed fromExample Composition 71, after nucleating at 630° C. for 2 hours andcerammed at 800° C. for 4 hours;

FIG. 18 is a graph showing an XRD trace of a glass-ceramic formed fromExample Composition 53, after nucleating at 630° C. for 2 hours andcerammed at 775° C. for 4 hours;

FIG. 19 is a graph shown an XRD trace of a glass-ceramic formed fromExample Composition 60, after nucleating at 630° C. for 2 hours andcerammed at 775° C. for 4 hours;

FIG. 20 is a FeO—Fe₂O₃—TiO₂ phase diagram showing the major solidsolutions;

FIG. 21 is a HAADF STEM image and the corresponding EDS map of thedifferent particles in a glass-ceramic formed from Example Composition53, after nucleating at 630° C. for 2 hours and cerammed at 800° C. for4 hours;

FIG. 22A is a graph showing the elemental composition of thecrystallites of glass-ceramics made from Example Composition 53;

FIG. 22B is a graph showing the elemental composition of thecrystallites of glass-ceramics made from Example Composition 71;

FIG. 23 is an electron energy-loss-near-edge-structure (ELNES) of Fe L₂₃edge showing the change of Fe from Fe³⁺ to Fe²⁺ at different cerammingtemperatures for glass-ceramics made from Example Composition 53;

FIG. 24 show HAADF STEM images of a glass-ceramic made from ExampleComposition 53, after being cerammed at different temperatures;

FIGS. 25A-C are graphs summarizing the image analysis of HAADF STEMimages of glass-ceramics made from Example Compositions 53 and 71;

FIG. 26 illustrates the ring-on-ring (ROR) biaxial flexure load tofailure of glass-ceramics made from Example Compositions 14 and 16,after ceramming at 700° C. for 4 hrs., compared to a known glass sample,before and after being ion exchanged;

FIG. 27 shows the abraded ring on ring biaxial flexure load to failureof glass-ceramics made from Example Compositions 14 and 16, afterceramming at 700° C. for 4 hrs., compared to a known glass sample, afterion exchange;

FIG. 28 shows a four point bend strength distribution of glass-ceramicsmade from Example Compositions 14 and 16, after ceramming at 700° C. for4 hrs., compared to a known glass sample, before and after ion exchange;

FIG. 29 shows a FeO—TiO₂—Fe₂O₃ phase diagram;

FIG. 30 shows the average area fraction of crystallites inglass-ceramics made from Example Compositions 14 and 16, as a functionof ceram temperature;

FIG. 31 shows the composition of crystallites in glass-ceramics madefrom Example Composition 14 as a function of ceram temperature brokendown into FeO, Fe₂O₃, MgO and TiO₂ via EELS and Fe L₂₃ edge spectra;

FIG. 32 shows the characteristic failure load and strength versus ionexchanged compressive stress in a known glass sample and glass-ceramicsmade from Example Compositions 14 and 16, after ceramming at 700° C. for4 hours.

DETAILED DESCRIPTION

Reference will now be made in detail to the present preferredembodiment(s), examples of which are illustrated in the accompanyingdrawings. While these aspects of embodiments and/or embodiments aredescribed in sufficient detail to enable those skilled in the art topractice this disclosure, it will nevertheless be understood that nolimitation of the scope of this disclosure is thereby intended.Alterations and further modifications of the features illustratedherein, and additional applications of the principles illustratedherein, which would occur to one skilled in the relevant art and havingpossession of this disclosure, are to be considered within the scope ofthis disclosure. Specifically, other aspects of embodiments and/orembodiments may be utilized, logical changes (e.g., without limitation,any one or more of chemical, compositional {e.g., without limitation,any one or more of chemicals, materials, . . . and the like},electrical, electrochemical, electromechanical, electro-optical,mechanical, optical, physical, physiochemical, . . . and the like) andother changes may be made without departing from the spirit or scope ofthis disclosure.

Strong and opaque materials (often exhibiting a black color) aredesirable for various applications. While known glass-ceramics have highstrength and toughness, the liquidus viscosity of such materials isoften too low to enable forming using fusion or slot draw methods.Alternative materials such as strengthened glasses provide high strengthand scratch resistance and are transparent to visible, microwave, andradio frequency radiation; however such materials are not well suitedfor mobile device backs where the goal is to hide the interior workingsof the device or appliance, yet allow wireless signals (e.g., cellular,WiFi, Bluetooth, etc.) to pass. Other alternative materials such asmetals are tough, strong and opaque, but block wireless transmission andscratch easily. Thus, there is a need for strong, scratch resistant,opaque materials that are transparent to microwave and radio frequencyradiation that are also economical to produce.

As mentioned above, strengthened glass ceramics provide good opacity andexhibit high retained strength and abraded strengths consistently above1450 MPa, but the liquidus viscosity exhibited by these materials isoften too low to enable pristine sheet formation via draw methods suchas fusion or slot draw. To resolve this issue, often such materials areground and polished after casting, pressing, or rolling, which addsadditional processes steps and cost, especially for complex shapes(e.g., 3-dimensional shapes). Known glass-ceramic materials, such asβ-spodumene glass-ceramics exhibit high liquidus viscosity (e.g., about2 kPa*s), which is usually sufficient for forming by pressing, but isstill an order of magnitude too low for fusion or slot drawingprocesses. Accordingly, the threshold liquidus viscosity for suchprocesses is believed to about more than 20 kPa*s.

As high strength, scratch resistance and low loss in the radio andmicrowave portion of the spectrum were also desirable. Suitableglass-ceramics should be capable of being chemically strengthened, forexample, by ion exchange processes.

To provide black, opaque materials, glass-ceramics exhibiting acrystalline phase with high absorption and low scattering across thevisible are desired. Opacity is believed to be most efficiently achievedwith a multiphase material so that both scattering and absorption worktogether to provide an intense color and the least transmission. Properselection of the composition (i.e., of the precursor composition,crystallizable glasses and/or glass-ceramics) and oxidation states ofthe precipitated (or crystalline) phases in formed glass-ceramics canprovide the most intense color and opacity. Moreover, to reducescattering within the glass ceramics, which results in loss and/orchange of color, the maximum allowable area fraction of the crystallinephase should be tailored. As used herein, the phrase “area fraction”means the percentage of an area of the glass-ceramic that includescrystallites. The area may be the surface area or an interior areahaving two-dimensions. The area size may be a minimum of about 1 inch by1 inch.

In known materials, desirable color and opacity is often achievedempirically by changing the starting composition of the precursorcomposition and crystallizable glass, nucleating at 630° C. andceramming at different temperatures in the range from about 675° C. to850° C., without the exact knowledge regarding the composition of thecrystallites in the crystalline phase, or the size and area fraction ofsuch crystallites. It is known that if a glass is saturated in aparticular phase, it can spontaneously precipitate that phase whencooled below the saturation temperature resulting in crystallization ofthat phase. As will be described herein, the crystallizable glasses andglass-ceramics described herein include crystallites having specificcompositional limits and/or area fraction and thus exhibit desirablecolor and opacity. The compositions of the crystallizable glasses andglass-ceramics described herein are tailored to provide such color andopacity, as well as lower liquidus temperatures which enables a largervariety of forming options to be utilized (e.g., fusion and slotdrawing).

The combination of opacity, color and high liquidus viscosity isdifficult to be achieved. For black, opaque materials often includehighly absorbing crystalline phases, whereas the opposite is desired forwhite, opaque materials. For white, opaque materials, the idealcrystalline phase exhibits minimal absorption and very high scattering.To achieve a deep rich black color, the chromophoric crystals should beas small as possible or index matched to the glass or glass phase in theglass-ceramics to prevent optical scattering, which would turn anotherwise black glass-ceramic to grey. The color intensity of theglass-ceramics can scale with the volume fraction of crystals; however,at high crystal concentrations when the crystalline components becomethe liquidus phase of the glass, the liquidus temperature will climbsharply causing the liquidus viscosity to plummet. Accordingly, simplyincreasing the area or volume fraction to achieve opacity or color cancome at the expense of liquidus viscosity.

The crystallizable glasses described herein exhibit high liquidusviscosities and can be heat-treated to yield opaque, saturated blackglass-ceramics with high strength. Accordingly, embodiments of theglass-ceramics described herein exhibit at least one of the followingattributes: opacity, intense black color, high indentation threshold,and the capability of being formed and specifically cerammed at a highviscosity, and embodiments of the crystallizable glasses describedherein exhibit at least one of the following attributes: high liquidusviscosity (e.g., greater than about 20 kPa*s) and transparency(sufficient to permit visual inspection for defects before ceramming).

Various aspects and/or embodiments of this disclosure relate tocrystallizable glasses and glass-ceramics, which may be ion-exchangeable(hereinafter “IXable”) or ion-exchanged (herein after “IX”). An IXableglass or glass-ceramic refers to a glass or glass-ceramic that can besubjected to an ion exchange surface treatment. The resulting glass orglass-ceramic may be referred to as an IX glass or glass-ceramic.

In one or more embodiments, crystallizable glasses having a composition,calculated on an oxide basis in percent by mole (mol %), including:

about 50-76 SiO₂;

about 4-25 Al₂O₃;

about 0-14 P₂O₅+B₂O₃;

about 0-33 R₂O;

about 0-5 of one or more nucleating agents; and

optionally, about 0-20 RO,

may be used to form the glass-ceramics described herein. Suchcomposition may be used in a fusion forming process to form theglass-ceramics and any intermediate glass article.

In one or more embodiments, the amount of SiO₂ in the compositions ofthe crystallizable glasses and/or glass-ceramics may be, in mol %, inthe range from about 50 to about 76, from about 50 to about 74, fromabout 50 to about 72, from about 50 to about 70, from about 50 to about68, from about 50 to about 67, from about 53 to about 76, from about 53to about 74, from about 53 to about 72, from about 53 to about 70, fromabout 53 to about 68, from about 53 to about 67, from about 56 to about76, from about 56 to about 74, from about 56 to about 72, from about 56to about 70, from about 56 to about 68, from about 56 to about 67, fromabout 58 to about 76, from about 58 to about 74, from about 58 to about72, from about 58 to about 70, from about 58 to about 68, from about 58to about 67, from about 62 to about 76, from about 62 to about 74, fromabout 62 to about 72, from about 62 to about 70, from about 62 to about68, and all ranges and sub-ranges therebetween. SiO₂ can be the mainconstituent of the composition and, as such, can constitute a matrix ofthe glass in the crystallizable glass and/or the glass-ceramic. Also,SiO₂ can serve as a viscosity enhancer for aiding in a glass'sformability while at the same time imparting chemical durability to theglass. Generally, SiO₂ can be present in amounts ranging from about 50mol % up to about 76 mol %. When SiO₂ exceeds about 76 mol %, a glass'smelting temperature can be impractically high for commercial meltingtechnologies and/or forming technologies.

In some embodiments, the amount of A1₂O₃ in the compositions of thecrystallizable glasses and/or glass-ceramics may be, in mol %, in therange from about 4 to about 25, from about 4 to about 20, from about 4to about 15, from about 4 to about 10, from about 5 to about 25, fromabout 5 to about 20, from about 5 to about 15, from about 5 to about 10,from about 10 to about 25, from about 10 to about 20, from about 10 toabout 18, from about 10 to about 15, from about 10 to about 14 or fromabout 8 to about 20, and all ranges and sub-ranges therebetween. In someaspects, Al₂O₃ can be present in amounts so as to impart a resistant todevitrification to crystallizable glasses while cooling from a liquidsuch as, for example, from about 4 mol % to about 25 mol %. When Al₂O₃exceeds about 25 mol %, the resultant mullite liquidus makes itdifficult to melt and form crystallizable glasses while Al₂O₃ belowabout 4 mol % can impart an insufficient level of resistant todevitrification to crystallizable glasses while cooling from a liquid.

The embodiments described herein may include B₂O₃, which may be present,in mol %, in the range from about 0 to about 12, from about 0 to about10, from about 0 to about 8, from about 0 to about 6, from about 0.1 toabout 12, from about 0.1 to about 10, from about 0.1 to about 8, fromabout 0.1 to about 6, from about 1 to about 12, from about 1 to about10, from about 1 to about 8, from about 1 to about 6, from about 3 toabout 12, from about 3 to about 10, from about 3 to about 8, or fromabout 3 to about 6, and all ranges and sub-ranges therebetween. In oneor more embodiments, the compositions of the crystallizable glassesand/or glass-ceramics described herein may include a combined amount ofP₂O₅ and B₂O₃ (P₂O₅+B₂O₃), in mol %, in the range from about 0 to about14, 0 to about 12, from about 0 to about 10, from about 0 to about 8,from about 0 to about 6, from about 3 to about 14, from about 3 to about12, from about 3 to about 10 and all ranges and sub-ranges therebetween.P₂O₅ and B₂O₃ may be included in the compositions because, at least inpart, of their capability of forming charged species in a network ofsuch composition. The charged species can interact with other cations ina manner so as to modify one or more properties of the resultantcrystallizable glasses and/or glass-ceramics. When P₂O₅+B₂O₃ exceedsabout 14 mol %, any benefits resulting from their additions might notincrease.

In some embodiments the total amount of R₂O in the compositions of thecrystallizable glasses and/or glass-ceramics may be, in mol %, in therange from about 0 to about 33, from about 0 to about 25, from about 0to about 20, from about 0.1 to about 33, from about 0.1 to about 25,from about 0.1 to about 20, from about 1 to about 33, from about 1 toabout 25, from about 1 to about 20, from about 1, from about 4 to about24 or from about 7 to about 20, and all ranges and sub-rangestherebetween. RO may be present in the compositions of thecrystallizable glasses and/or glass-ceramics in an amount, in mol %, inthe range from about 0 to about 20, from about 0 to about 15, from about0 to about 10, from about 0 to about 8, from about 0 to about 5, fromabout 0.1 to about 20, from about 0.1 to about 15, from about 0.1 toabout 10, from about 0.1 to about 8, or from about 0.1 to about 5 andall ranges and sub-ranges therebetween. R₂O can modify the viscosity ofthe composition such that a crystallizable glass exhibiting a highliquidus viscosity can be provided, while at the same time reduce themelting temperature of the crystallizable glasses and/or enable shorterthermal treatments. Also, R₂O can be used to modify viscosity of theresultant glass-ceramics. When R₂O exceeds about 33 mol %, liquidusviscosity be impractically low for commercial melting technologiesand/or forming technologies.

In some embodiments, the compositions of the crystallizable glassesand/or glass-ceramics may include the following compositional criteria:R₂O+RO—Al₂O₃ in the range from about −4 to about 10, from about −2 toabout 8, −2 to about 5, from about −1 to about 5, or from about 0 toabout 2.5, and all ranges and sub-ranges therebetween. In otherinstances, the compositions of the crystallizable glasses and/orglass-ceramics may include the following composition criteria: R₂O—Al₂O₃in the range from about −8 to about 8, from about −4 to about 4, fromabout −2 to about 3, from about −2 to about 2 or from about −1 to about1.5.

In some embodiments, R₂O may include one or more of Li₂O, Na₂O, L₂O,Rb₂O, Cs₂O, Cu₂O, and Ag₂O. In one or more embodiments, Cu₂O is formedby including CuO in the batch for the crystallizable glass. In specificembodiments, R₂O may include one or more of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O,and Cu₂O. In a more specific embodiment, R₂O may include one or more ofLi₂O, Na₂O, and K₂O. In an even more specific embodiment, R₂O mayinclude one or more of Na₂O, and K₂O. Where Li₂O is utilize, it may bepresent in an amount, in mol %, in the range from about 0 to about 20 orfrom about 0 to about 5. Where Na₂O is included, it may be present in anamount, in mol %, in the range from about 0 to about 20 or from about 5to about 18. Where K₂O is included, it may be present in an amount, inmol %, in the range from about 0 to about 10 or from about 0 to about 5.

In some embodiments, RO can include one or more of MgO, CaO, SrO, BaO,and ZnO. In one or more specific embodiments, RO can include one or moreof MgO, CaO, SrO, and BaO. In even more specific embodiments, RO caninclude one or more of MgO, CaO, and SrO. In one or more embodiments,MgO is present in an amount, in mol %, in the range from about 0 toabout 10 or from about 1 to about 3. In one or more embodiments, CaO ispresent in an amount, in mol %, in the range from about 0 to about 10 orfrom about 0 to about 2.

In one or more embodiments, the compositions of the crystallizable glassand/or glass-ceramics may also include Fe₂O₃ in an amount, in mol %, inthe range from about 0.25 to about 5 or from about 0.5 to about 2. Theratio of Fe₂O₃/TiO₂ and/or Fe₂O₃/MgO may be specified. In someembodiments, the ratio may Fe₂O₃/TiO₂ may be about 2 or less, about 1.5or less, or about 1.2 or less. In other embodiments, the ratio mayFe₂O₃/MgO may be about 2 or less, about 1.8 or less, about 1.6 or less,about 1.5 or less, or about 1.2 or less.

The compositions of the crystallizable glass and/or glass-ceramics mayalso include one or more nucleating agents in an amount, in mol %, inthe range from about 0 to about 5, from about 1 to about 4, or fromabout 1 to about 3, and all ranges and sub-ranges therebetween. In someembodiments, the one or more nucleating agents may include TiO₂ and/orZrO₂. On an oxide basis in mol %, TiO₂ can be included in thecompositions of the crystallizable glass and/or glass-ceramics in anamount up to about 5, up to about 4, up to about 3 and all ranges andsub-ranges therebetween. In specific embodiments, TiO₂ may be present,in mol %, in an amount in the range from about 0.25 to about 5 or fromabout 0.5 to about 2. Alternatively, calculated on an oxide basis in mol%, ZrO₂ can included in the compositions of the crystallizable glassand/or glass ceramics in an amount up to about 3, or up to about 2 andall ranges and sub-ranges therebetween. When the one or more nucleatingagents include TiO₂ and ZrO₂, the combined amount thereof (TiO₂+ZrO₂)can include up to about 5 mol %, up to about 4 mol %, and in some cases,the amount of ZrO₂ in the combination can be up to about 3 mol % or upto about 2 mol %, all calculated on an oxide basis. The one or morenucleation agents are incorporated to facilitate nucleation and/orgrowth of at least crystalline phase and any desired one or more minorcrystalline phases during thermal treatment (e.g., nucleation and/orcrystallization) of the crystallizable glasses described herein. When anamount of one or more nucleation agents exceeds about 5 mol %, there canbe a diminishing return on the benefit of adding more. In someembodiments, the inclusion of TiO₂ as a nucleation agent is desirablewhen the formation of one or more Ti-containing crystalline phases isdesired. In other embodiments, the inclusion of ZrO₂ as a nucleationagent can increase nucleation efficiency. In some specific embodiments,a minimum mol % sum [TiO₂+SnO₂] is in excess of 1 mole %. In some cases,effective amounts of this mol % sum [TiO₂+SnO₂] are formulated as aningredient of crystallizable glasses so that nucleation in an effectivemanner occurs and growth is achieved to a preselected and appropriatecrystal phase assemblage. The amount of TiO₂ above 5 mole % can beundesirable as the resultant high rutile liquidus has the potential ofincreasing difficulties during shape forming of crystallizable glassesand/or glass-ceramics. In some embodiments, SnO₂ may be present in anamount, in mol %, in the range from about 0 to about 0.5 or from about 0to about 0.2.

The glass-ceramics of one or more embodiments exhibit low crystallinity.For example, the glass-ceramics may include one or more crystallinephases, which can comprise about 20 wt % or less of the glass-ceramic.In some embodiments, the crystalline phase can be about 15 wt % or less,about 10 wt % or less, or about 5 wt % or less of the glass-ceramic. Inone or more embodiments, the area fraction of the crystallites may beabout 20% or less, 15% or less, 10% or less or even 8% or less. In someembodiments, the area fraction may be in the range from about 0.1% toabout 20%, from about 0.1% to about 18%, from about 0.1% to about 16%,from about 0.1% from about 15%, from about 0.1% to about 14%, from about0.1% to about 13%, from about 0.1% to about 12%, from about 0.1% toabout 11%, from about 0.1% to about 10%, from about 0.1% to about 9%,from about 0.1% to about 8%, from about 0.1% to about 7%, from about0.1% to about 6%, from about 0.1% to about 5%, and all ranges andsub-ranges therebetween.

The glass-ceramics disclosed herein may include one or more oxidecrystalline phases. In some embodiments, one or more silicates aresubstantially absent from the one or more oxide crystalline phases.Exemplary oxide crystalline phases that may be present in theseglass-ceramics include one or more of TiO₂, FeO, Fe₂O₃, Fe₃O₄, MgO,FexTiyOz, FexTiyMgzOa and ZnO and, optionally, one or more transitionmetal oxides selected from one or more of V, Cr, Mn, Co, Ni, and Cu.

The glass-ceramics of one or more embodiments include one or morecrystalline phases such as highly absorbing compounds in theFe₂O₃—TiO₂—MgO system (e.g., magnetite, pseudobrookite, and/or ε-Fe₂O₃).In some embodiments, the glass-ceramics have crystallites that includeMgO, Fe₂O₃, TiO₂ and/or combination thereof. Specific embodiments mayinclude crystallites including Mg²⁺, Fe²⁺+Fe³⁺, Ti⁴⁺ oxides andcombinations thereof.

In some embodiments, the crystallites can include, in mole percent, MgOin an amount in the range from about 0 to about 60, from about 1 toabout 60, from about 5 to about 60, from about 10 to about 60, fromabout 15 to about 60, from about 20 to about 60, from about 1 to about55, from about 1 to about 50, from about 1 to about 45, from about 1 toabout 40, from about 5 to about 50, from about 5 to about 45, from about10 to about 40, and all ranges and sub-ranges therebetween.

In some instances, the crystallites can include, in mole percent, Fe₂O₃in an amount in the range from about 5 to about 75, from about 5 toabout 70, from about 5 to about 65, from about 5 to about 60, from about10 to about 75, from about 15 to about 65, from about 15 to about 60,from about 15 to about 75, from about 15 to about 70, from about 15 toabout 65, from about 15 to about 60, and all ranges and sub-rangestherebetween. In some instances, the crystallites can include Fe₂O₃ inan amount up to about 100 mole percent (e.g., from 40 to 100 molepercent, from 50 to 100 mole percent, or from 60 to 100 mole percent).In such embodiments, the phases can include ferrites such as magnetite(Fe₃O₄), CoFe₂O₄, MnFe₂O₄, NiFe₂O₄, and other magnetic and non-magneticferrites.

In other instances, the crystallites can include, in mole percent, TiO₂in an amount in the range from about 0 to 75, 5 to 75, 10 to about 75,from about 10 to about 70, from about 10 to about 65, from about 10 toabout 60, from about 10 to about 55, from about 15 to about 75, fromabout 15 to about 70, from about 15 to about 65, from about 15 to about60, from about 15 to about 55, from about 20 to about 75, from about 20to about 70, from about 20 to about 65, from about 20 to about 60, fromabout 20 to about 55, and all ranges and sub-ranges therebetween.

In one or more embodiments, the glass-ceramics include a ε-Fe₂O₃ phasethat exhibits extensive solid solution (ss) between Fe₂O₃ and MgTiO₃.The blackness and opacity of these ε-Fe₂O₃ glass-ceramics peaked at aceram temperature of 750° C. where the Fe²⁺ in the crystallites wasmaximized, resulting in peak Fe²⁺—Ti⁴⁺ charge transfer absorption. Theliquidus viscosity of the crystallizable glasses described herein wasalso increased to about 100 kPa*s or more, by optimizing the compositionof the crystallizable glasses and minimizing the amount ofcrystallinity, thereby enabling fusion-formability. Thesefusion-formable crystallizable glasses and glass-ceramics also exhibitedhigh strength properties, after being strengthened (e.g., by ionexchange processes).

In any of these embodiments, the one or more crystalline phases caninclude crystallites having a size of at least 5 nm and less that about300 nm, less that about 200 nm, less that about 100 nm, or less thanabout 50 nm, and all ranges and sub-ranges therebetween The minimum sizeof the crystallites may be about 5 nm or about 10 nm. As used herein,the term “size” with reference to crystallites includes the length ofthe longest dimension of the crystallites. In some cases, the size ofthe crystallites may be about 80 nm or less, about 70 nm or less, about60 nm or less, about 50 nm or less. In some cases, the crystallites mayhave a size in the range from about 5 nm to about 100 nm or from about 5nm to about 50 nm.

As described herein, some glass-ceramics are formulated to be capable ofbeing subjected to an ion exchange treatment to provide IXglass-ceramics, which include least one surface under a compressivestress (σs) of at least about 200 MPa or at least about 700 MPa. In someembodiments, the compressively stressed surface can extend into theglass-ceramic and have a depth of layer (DOL) of at least about 1 μm, atleast about 20 μm, or at least about 60 μm. For example, where the IXglass-ceramics have a total thickness in the range from about 0.7millimeter (mm) up to 5 mm, the DOL may be in the range from about 20 μmto about 150 μm, from about 30 μm to about 120 μm, from about 40 μm toabout 100 μm. In specific instances, the total thickness of the IXglass-ceramics may be in the range from about 0.7 mm to about 2 mm, orfrom about 0.7 mm to 1.3 mm. In some embodiments, the glass-ceramicsdisclosed herein are subjected to ion exchange treatment to impartantimicrobial properties to the glass-ceramics and/or IX glass-ceramicsdescribed herein. In such embodiments, the glass-ceramics and/or IXglass-ceramics are immersed in a bath including antimicrobial componentssuch as AgNO₃, and/or a Cu-containing salt such as CuCl/CuSO₄ and/oraqueous CuCl. A mixture of CuCl and KCl, a mixture of CuCl and NaCl,and/or a mixture of all three of CuCl, KCl and NaCl may also be utilizedfor a Cu-containing salt bath.

The IX glass-ceramics according to one or more embodiments, which havebeen subjected to an ion exchange treatment, exhibit a Vickers mediancrack initiation threshold of at least 5 kilograms force (kgf), at least10 kgf, at least 15 kgf, or at least 20 kgf, and all range andsub-ranges therebetween. In one or more embodiments, the crystallizableglasses and/or glass-ceramics described herein exhibit high strength.For example, in some embodiments, the crystallizable glasses and/orglass-ceramics exhibit a flexural strength, as measured by ring on ring(ROR), in the range from about 2000 N to about 4000 N, from about 2000 Nto about 3800 N, from about 2000 N to about 3600 N, from about 2000 N toabout 3400 N, from about 2000 N to about 3200 N, from about 2000 toabout 3000 N, from about 2100 N to about 3000 N, from about 2200 N toabout 3000 N, from about 2300 N to about 3000 N, from about 2400 N toabout 3000N, from about 2500 N to about 3000 N, from about 2600 N toabout 3000 N, from about 2700 N to about 3000 N, from about 2750 N toabout 3000 N, from about 2800 N to about 3000 N, from about 2850 N toabout 3000 N, from about 2900 N to about 3000 N, and all ranges andsub-ranges therebetween. In specific embodiments, the crystallizableglasses and/or glass-ceramics exhibit a flexural strength, as measuredby ring on ring (ROR), in the range from about 200 kgf to about 400 kgfbreak load. In even more specific embodiments, the crystallizableglasses and/or glass-ceramics exhibit a flexural strength, as measuredby ring on ring (ROR), in the range from about 200 kgf to about 380 kgf,from about 200 kgf to about 360 kgf, from about 200 kgf to about 340kgf, from about 200 kgf to about 320 kgf, from about 200 kgf to about300 kgf, from about 210 kgf to about 400 kgf, from about 220 kgf toabout 400 kgf, from about 230 kgf to about 400 kgf, from about 240 kgfto about 400 kgf, from about 250 kgf to about 400 kgf, from about 260kgf to about 400 kgf, or from about 270 kgf to about 400 kgf break load,and all ranges and sub-ranges therebetween.

In one or more embodiments, the crystallizable glasses and/orglass-ceramics exhibit a flexural strength, as measured by abraded ringon ring (aROR) and after being abraded with about 1 ml of SiC particlesat 34 kPa pressure, in the range from about 700 N to about 1500 N, fromabout 750 N to about 1500 N, from about 800 N to about 1500 N, fromabout 850 N to about 1500 N, from about 900 N to about 1500 N, fromabout 950 N to about 1500 N, from about 1000 to about 1500 N, from about900 N to about 1450 N, from about 900 N to about 1400 N, from about 900N to about 1350 N, from about 900 N to about 1300 N, from about 900 N toabout 1250 N, from about 900 N to about 1200 N, from about 900 N toabout 1150 N, from about 900 N to about 1100, and all ranges andsub-ranges therebetween. In other embodiments, the crystallizableglasses and/or glass-ceramics exhibit a flexural strength, as measuredby abraded ring on ring (aROR) and after being abraded with about 1 mlof SiC particles at 34 kPa pressure, in the range from about 100 kgf toabout 200 kgf, from about 100 kgf to about 190 kgf, from about 100 kgfto about 180 kgf, from about 100 kgf to about 170 kgf, from about 100kgf to about 160 kgf, from about 100 kgf to about 150 kgf, from about110 kgf to about 200 kgf, from about 120 kgf to about 200 kgf, fromabout 130 kgf to about 200 kgf, from about 140 kgf to about 200 kgf, andall ranges and sub-ranges therebetween.

In one or more embodiments, the crystallizable glasses and/orglass-ceramics exhibit an edge strength, as measured by 4 point bend, inthe range from about 600 MPa to about 1000 MPa, from about 600 MPa toabout 950 MPa, from about 600 MPa to about 900 MPa, from about 600 MPato about 850 MPa, from about 600 MPa to about 800 MPa, from about 600MPa to about 750 MPa, from about 600 MPa to about 700 MPa, from about650 MPa to about 1000 MPa, from about 700 MPa to about 1000 MPa, fromabout 750 MPa to about 1000 MPa, from about 800 MPa to about 1000 MPa,and all ranges and sub-ranges therebetween.

In one or more embodiments, the glass-ceramics, whether IX or not,exhibit a color presented in CIELAB color space coordinates for CIEilluminant D65 determined from reflectance spectra measurements using aspectrophotometer with SCE with an a* coordinate from about −2 to about+8 and a b* coordinate from about −7 to about +20. In some embodiments,the a* coordinate exhibited by the glass-ceramics may be from about −3to about +3, from about −2 to about +3, from about −1 to about +3, fromabout −2 to about +2 or from about −1 to about +1. The b* coordinateexhibited by the glass-ceramics may be from about −10 to about +10, fromabout −8 to about +8, from about −7 to about +7, from about −6 to about+6, from about −5 to about +5, from about −4 to about +4, from about −3to about +3, from about −2 to about +3, from about −2 to about +2, fromabout −1 to about +1 and all ranges and sub-ranges therebetween. In someembodiments, the glass-ceramics may exhibit a L* coordinate that canapproach dark colors and/or black while in other of these aspects the L*coordinate can approach light colors and/or white. For example for darkcolors and/or black, presented in CIELAB color space coordinates for CIEilluminant D65 determined from reflectance spectra measurements using aspectrophotometer with SCE, the glass-ceramics may exhibit a L*coordinate from about 0 to about 30, from about 5 to about 30, fromabout 10 to about 30, from about 12 to about 30, from about 14 to about30, from about 16 to about 30, from about 0 to about 20, from about 0 toabout 15, from about 0 to about 10, from about 0 to about 5, or fromabout 0 to about 3.

The glass-ceramics described herein may also exhibit an average %transmission of at least one wavelength, λ_(T), in an interval ofwavelengths from about 390 nm to about 1000 nm of less than about 50,less than about 40, less than about 30, less than about 20 or less thanabout 10. In some embodiments, the % transmission of at least onewavelength, 4, in an interval of wavelengths from about 390 nm-2000 nmor from about 390 nm-1000 nm, may be less than about 5, less than about4, less than about 3, less than about 2, less than about 1 and about 0.Alternatively, various glass-ceramic embodiments can have an averagevalue in percent (%) of transmission over a λ interval from about 390 nmto about 1000 nm

$\lbrack {{\begin{matrix}{2500\mspace{14mu}{nm}} \\{390\mspace{14mu}{nm}}\end{matrix}{T_{avg}(\%)}} = {\frac{1}{( {2500 - {390\mspace{14mu}{nm}}} )}{\sum\limits_{390\mspace{14mu}{nm}}^{2500\mspace{14mu}{nm}}{T_{\lambda}\{ \% \}}}}} \rbrack$of less than about 50, less than about 40, less than about 30, less thanabout 20 or less than about 10. Over wavelengths from about 200 nm toabout 780 nm, the transmission of some embodiments may be less thanabout 10%, or less than about 5%. In some instances, over a 100 nmwavelength segment along the wavelength range from about 200 nm to about780 nm, the average transmission may be less than about 5%, less than1%, or less than 0.1%. Such average % transmissions recited herein maybe exhibited by glass-ceramics having a thickness of about 0.8 mm.

The glass-ceramics disclosed herein may exhibit certain dielectricproperties. That is, in addition to such glass-ceramics having one ormore preselected colors, which additionally might be tunable or havebeen tuned, for example, to impart one or more aesthetic colors, suchglass-ceramics can possess advantageous dielectric properties. In one ormore embodiments, the glass-ceramics may exhibit a loss tangent over afrequency ranging from about 0.5-3.0 GHz at about 25° C. and/or adielectric constant over a frequency ranging from about 0.5-3.0 GHz atabout 25° C.

Exemplary glass-ceramics may be formulated to be capable of being formedfrom a molten state using one or more of a float method, a slot drawmethod, and/or a fusion method and, optionally, subsequently a redrawmethod and/or roll out method. To that end, in some embodiments,crystallizable glasses have compositions formulated to form theglass-ceramics exhibit a liquidus viscosity (η_(lqds)) of at least about20 kP, at least about 50 kP, at least about 100 kP, or at least about150 kP, and all ranges and sub-ranges therebetween. In some embodiments,the liquidus viscosity of the composition may be in the range from about20 kP to about 100000 kP, from about 50 kP to about 100000 kP, or fromabout 1000 kP to about 100000 kP. In some other aspects, suchcompositions are formulated to exhibit a liquidus temperature (T_(lqds))of less than about 1600° C., less than about 1400° C., less than about1300° C., less than about 1200° C. or even less than about 1100° C.,less than about 1000, less than about 900 C. In some embodiments, thecompositions are formulated to exhibit a T_(lqds) of about 650° C. orgreater.

The crystallizable glass compositions described herein may be formulatedfor ease of processing (e.g., melting, processing, forming . . . etc.).In such embodiments, the crystallizable glasses may exhibit an average %transmission of at least one wavelength, λ_(T), in an interval ofwavelengths from about 390 nm-2000 nm or from about 390 nm-1000 nm, ofleast about 90, at least about 70 or at least about 50. Thecrystallizable glasses of some embodiments may exhibit an average valuein percent (%) of transmission over a λ interval from about 390 nm toabout 1000 nm

$\lbrack {{\begin{matrix}{2500\mspace{14mu}{nm}} \\{390\mspace{14mu}{nm}}\end{matrix}{T_{avg}(\%)}} = {\frac{1}{( {2500 - {390\mspace{14mu}{nm}}} )}{\sum\limits_{390\mspace{14mu}{nm}}^{2500\mspace{14mu}{nm}}{T_{\lambda}\{ \% \}}}}} \rbrack$of at least about 40, of at least about 50, at least about 70, or atleast about 90. Such average % transmissions recited herein may beexhibited by crystallizable glasses having a thickness of about 0.8 mm.Over a wavelength range from about 390 nm to about 780 nm, thetransmission of some embodiments is about 30% or greater, or up to 90%.In some instances, over a 100 nm wavelength segment along the wavelengthrange from about 200 nm to about 780 nm, the average transmission isgreater than 30%, greater than 70%, or up to about 90%.

The crystallizable glasses of one or more embodiments, may be formulatedto be crystallizable at one or more preselected temperatures for one ormore preselected times to a glass-ceramic, such as those describedherein. Accordingly, in some specific embodiments, the crystallizableglasses may exhibit a viscosity (η) at which crystals are grown, of atleast about 10E¹⁰P, at least about 10E⁹P, or at least about 10E⁸P.

In one or more embodiments, the crystallizable glass may have specificoptical properties. For example, the crystallizable glasses may betransparent or substantially transparent. In some cases, thecrystallizable glasses may exhibit an average transmission of at leastabout 10% or at least about 50% in the visible-to-near-IR spectrum inthe wavelength range from about 375 nm to about 2000 nm. In some cases,the average transmission can be as high as 60%, 70% or even 80%.

The crystallizable glasses described herein may optionally include oneor more colorants. The amount of the colorants can vary and can include,up to about 5.2 mol %, up to about 4 mol %, up to about 2.8 mol %, or upto about 1.5 mol % of the crystallizable glass, calculated on an oxidebasis.

The one or more colorants can be formulated to provide one or more Fe²⁺sources, one or more Fe³⁺ sources and/or the combination of Fe²⁺ andFe³⁺ sources to the crystallizable glasses and/or resultingglass-ceramics formed from the crystallizable glasses. In otherembodiments, such one or more colorants can be formulated to provide oneor more iron oxides and one or more other transition metal oxides tocrystallizable glasses and/or resulting glass-ceramics formed therefrom.In still other embodiments, such one or more one or more colorants canbe, for example, one or more of TiO₂, FeO, Fe₂O₃, Fe₃O₄, MgO, and ZnOand, optionally, one or more transition metal oxides selected from oneor more of V, Cr, Mn, Co, Ni, and Cu. The one or more other transitionmetal oxides can be an oxide of one or more of Ti, Mn, Co, and Cu. Instill other embodiments, the one or more one or more colorants can beformulated to provide one or more multivalent metal oxides and,optionally, one or more reducing agents to crystallizable glasses and/orprogeny glass-ceramics. In such embodiments, the one or more multivalentmetal oxides can include an oxide of one or more of Ti, Mn, Fe, Co, Cu.In each of these embodiments, one or more silicates may be substantiallyabsent from the one or more oxide crystalline phases.

In some embodiments, Fe and/or Sn may be included as part of a finingpackage during glass formation. Where a Sn-free glass is desired, Fe maybe used in the fining package.

Another aspect of this disclosure pertains to process(es) for making thecrystallizable glasses and glass-ceramics described herein. Theprocesses include providing such crystallizable glasses andglass-ceramics that exhibit one or more preselected colors. In someembodiments, raw materials for making crystallizable glasses and progenyglass-ceramics can be formulated to provide these preselected color(s)sthat can be tunable or have been tuned.

In other embodiments, the processes for making the crystallizableglasses and/or glass-ceramics described herein including formulating thecrystallizable glasses in such manner to facilitate processing usingmechanized means, including continuous, semi-continuous, and/orbatch-wise processing in a manufacture of shaped parts of thecrystallizable glasses and glass-ceramics described herein. Non-limitingexamples of shaped parts can range from sheets or fibers to one or morecomplex three dimensional (3D) shapes such as, for example, a concaveshape, a convex shape, or any other desired predetermined geometry . . .etc. For example in the case of sheets, one or more crystallizable glasssheets can be formed from a molten state by any one of a float method ora down draw methods, such as a slot draw method or a fusion method. Ifdesirable, such crystallizable glass sheets might be then subjected toone or more redraw methods and/or one or more roll out methods. Such oneor more redraw methods and/or one or more roll out methods might beperformed while the crystallizable glass sheets are in a viscous statebetween about 10E^(3.5)P to 10E^(7.6)P.

In one or more embodiments, the crystallizable glasses andglass-ceramics described herein may be formed using any one of a floatprocess, a fusion down-draw process, a slot-draw process, or any othersuitable process typically used for forming crystallizable glassessubstrates from a batch of glass raw materials. As a specific example,the crystallizable glasses described herein might be formed into glasssubstrates using a fusion down-draw process. Such fusion down-drawprocesses utilize a drawing tank that has a channel for accepting moltenglass raw material. The channel has weirs that open at the top along thelength of the channel on both sides of the channel. When the channelfills with molten glass, the molten glass overflows the weirs and, dueto gravity, the molten glass flows down the outside surfaces of thedrawing tank as two flowing glass surfaces. These outside surfacesextend downwardly and inwardly while joining at an edge below thedrawing tank. The two flowing glass surfaces join at this edge and fuseto form a single flowing sheet of molten glass that may be further drawnto a desired thickness. The fusion down-draw process produces glasssheets with highly uniform, flat surfaces as neither surface of theresulting glass sheet is in contact with any part of the fusionapparatus.

In some embodiments, the liquidus viscosity of the crystallizable glassmay be tuned to enable use of a fusion down-draw process in forming theglasses described herein. The liquidus viscosity may be modified tolimit or minimize the crystal growth in the glass during formation.

As an alternative specific example, the one or more crystallizableglasses of this disclosure and described herein may be formed using aslot-draw process in which molten glass raw materials are supplied to adrawing tank. The bottom of the drawing tank has an open slot with anozzle that extends the length of the slot. The molten glass flowsthrough the slot/nozzle and is drawn downward as a continuous sheet andinto an annealing region.

The molten glass raw materials are formulated to produce thecrystallizable glasses described herein upon fining and homogenizationof the molten glass compositions at a temperature between about 1400° C.and about 1650° C.

In one or more embodiments, the processes for making the glass-ceramicsdescribed herein includes heat treating the crystallizable glasses atone or more preselected temperatures for one or more preselected timesto induce crystallization (i.e., nucleation and growth) of one or morecrystalline phases (e.g., having one or more compositions, amounts,morphologies, sizes or size distributions, etc.). In one or morespecific embodiments, the heat treatment can include (i) heatingcrystallizable glasses at a rate of 1-10° C./min to a nucleationtemperature (Tn) in the range from about 600° C. to about 750° C. (e.g.,630° C.); (ii) maintaining the crystallizable glasses at the nucleationtemperature for a time in the range from between about ¼ hr to about 4hr to produce nucleated crystallizable glasses; (iii) heating thenucleated crystallizable glasses at a rate in the range from about 1°C./min to about 10° C./min to a crystallization temperature (Tc) in therange from about 575° C. to about 900° C. (e.g., from about 700° C. toabout 775° C.); (iv) maintaining the nucleated crystallizable glasses atthe crystallization temperature for a time in the range from about ¼ hrto about 4 hr to produce the glass-ceramics described herein; and (v)cooling the formed glass-ceramics to room temperature. As used herein,the term crystallization temperature may be used interchangeably withceram or ceramming temperature. In addition, the terms “ceram” or“ceramming” may be used to refer to steps (iii), (iv) and optionally(v), collectively.

Temperature-temporal profile of heat treatment steps (iii) and (iv), inaddition to crystallizable glass compositions, are judiciouslyprescribed so as to produce one or more of the following desiredattributes: crystalline phase(s) of the glass-ceramics, proportions ofone or more predominate crystalline phases and/or one or more minorcrystalline phases and residual glass, crystal phase assemblages of oneor more predominate crystalline phases and/or one or more minorcrystalline phases and residual glass, and grain sizes or grain sizedistributions among one or more predominate crystalline phases and/orone or more minor crystalline phases, which in turn may influence thefinal integrity, quality, color, and/or opacity, of resultant formedglass-ceramics.

The resultant glass-ceramic sheets can then be reformed by pressing,blowing, bending, sagging, vacuum forming, or other means into curved orbent pieces of uniform thickness. Reforming can be done before thermallytreating or the forming step can also serve as a thermal treatment stepwhere both forming and thermally treating are performed substantiallysimultaneously. For example a crystallizable glass might be formed intoa 3D shape by forming the crystallizable glass into tubing and thermallytreating the 3D crystallizable glass to transforming it into black, 3Dglass-ceramic tubing. In some embodiments, the forming might precede thetransforming, or the transforming might precede the forming, or thetransforming might occur substantially simultaneously with the forming.

In yet other embodiments, the compositions used to form thecrystallizable glasses and/or glass-ceramics can be formulated, forexample, so that the glass-ceramics described herein are capable ofbeing transformed to IX glass-ceramics using one or more ion exchangetechniques. In these embodiments, ion exchange can occur by subjectingone or more surfaces of such glass-ceramics to one or more ion exchangebaths, having a specific composition and temperature, for a specifiedtime period to impart to the one or more surfaces with compressivestress(es) (σs). The compressive stresses can include one or moreaverage surface compressive stress (CS), and/or one or more depths ofcompressive stresses (which may be referred to as one or more depths oflayer (DOL)).

The bath(s) used in the ion exchange process represent an ion sourcehaving one or more ions having an ionic radius larger than the ionicradius of one or more ions present in the glass-ceramic (and, moreparticularly, the ions present in at least one surface of theglass-ceramic). During immersion of the glass-ceramic into the bath, theions in the glass-ceramic having smaller radii can replace or beexchanged with ions having larger radii. This exchange may befacilitated or achieved by controlling the bath and/or glass-ceramictemperature within a range of temperatures at which ion inter-diffusion(e.g., the mobility of the ions from between bath and the glass-ceramic)is sufficiently rapid within a reasonable time (e.g., between about 1hr. and 64 hrs. or from 4-16 hrs., ranging at between about 300° C. and500° C. or from 400° C.-430° C.). Also, typically such temperature isbelow the glass transition temperature (Tg) of any glass of aglass-ceramic. Some exemplary ions that may be exchanged between thebath and the glass-ceramic include sodium (Na⁺), lithium (Li⁺),potassium (K⁺), rubidium (Rb⁺), and/or cesium (Cs⁺) ions. In onescenario, the bath may include sodium (Na⁺), potassium (K⁺), rubidium(Rb⁺), and/or cesium (Cs⁺) ions, which may be exchanged for lithium(Li⁺) ions in the glass-ceramic. Alternatively, ions of potassium (K⁺),rubidium (Rb⁺), and/or cesium (Cs⁺) in the bath can be exchanged forsodium (Na⁺) ions in the glass-ceramic. In another scenario, ions ofrubidium (Rb⁺) and/or cesium (Cs⁺) in the bath may be exchanged forpotassium (K⁺) ions in the glass-ceramics.

Some examples of ion sources include one or more gaseous ion sources,one or more liquid ion sources, and/or one or more solid ion sources.Among one or more liquid ion sources are liquid and liquid solutions,such as, for example molten salts. For example for the aboveion-exchange examples, such molten salts can be one or more alkali metalsalts such as, but not limited to, one or more halides, carbonates,chlorates, nitrates, sulfites, sulfates, or combinations of two or moreof the proceeding. In one example, suitable alkali metal salts caninclude potassium nitrate (KNO₃), sodium nitrate (NaNO₃) and thecombination thereof. It should be noted that in addition to single stepIX processes, multiple step IX processes can be utilized to provide aspecific CS to the surface of the glass-ceramic and thus, enhance aglass-ceramic's performance. In some embodiments, single step IXprocesses can be accomplished by exchanging ion (particularlylithium-for-sodium ion exchange) into a surface of the glass-ceramic byplacing a glass-ceramic article in NaNO₃ baths at between about 300° C.and 500° C. for between about lhr and 64 hr. In other embodiments,single step IX processes can be accomplished by placing a glass-ceramicarticle in a mixed potassium/sodium baths at (e.g. a 80/20 KNO₃/NaNO₃bath, a 60/40 KNO₃/NaNO₃ bath, or even a 50/50 KNO₃/NaNO₃ bath . . .etc.) at between about 300° C. and 500° C. for between about 1 hr and 64hr. In still other embodiments, two-step IX process can be accomplishedby first placing a glass-ceramic article in a Li-containing salt bath(e.g. the molten salt bath can be a high temperature sulfate salt bathcomposed of Li₂SO₄ as a major ingredient, but diluted with Na₂SO₄, K₂SO₄or Cs₂SO₄ in sufficient concentration to create a molten bath) betweenabout 300° C. and 500° C. for between about 1 hr and 64 hr followed byplacing the IX, glass-ceramic in a Na-containing salt bath between about300° C. and 500° C. for between about 1 hr and 64 hr. The first step ofthe two step IX process functions to replace the larger sodium ions inthe in the glass-ceramic's at least one surface with the smaller lithiumions found in the Li-containing salt bath. The second step of the twostep IX process functions to exchange Na into in the glass-ceramic's atleast one surface.

In a more particular embodiment, the glass-ceramics may have to athickness (e.g., in the range from about 0.7 mm up to about 5 mm, fromabout 0.7 mm to about 2 mm, or from about 0.7 mm to about 1.3 mm) andcompressive layer having an average surface compressive stress of about500 MPa or greater and a DOL of about 40 μm or greater.

Various articles may incorporate or utilize the crystallizable glassesand/or glass-ceramics described herein. For example, covers and/orhousings used in electronic devices might be formed using thecrystallizable glasses and/or glass-ceramics. In still yet otherembodiments, the crystallizable glasses and glass-ceramics might be usedin a variety of electronic devices or portable computing devices, whichmight be configured for wireless communication, such as, computers andcomputer accessories, such as, “mice”, keyboards, monitors (e.g., liquidcrystal display (LCD), which might be any of cold cathode fluorescentlights (CCFLs-backlit LCD), light emitting diode (LED-backlit LCD) . . .etc., plasma display panel (PDP) . . . and the like), game controllers,tablets, thumb drives, external drives, whiteboards . . . etc.; personaldigital assistants (PDAs); portable navigation device (PNDs); portableinventory devices (PIDs); entertainment devices and/or centers, devicesand/or center accessories such as, tuners, media players (e.g., record,cassette, disc, solid-state . . . etc.), cable and/or satellitereceivers, keyboards, monitors (e.g., liquid crystal display (LCD),which might be any of cold cathode fluorescent lights (CCFLs-backlitLCD), light emitting diode (LED-backlit LCD) . . . etc, plasma displaypanel (PDP) . . . and the like), game controllers . . . etc.; electronicreader devices or e-readers; mobile or smart phones . . . etc. Asalternative examples, the crystallizable glasses and glass-ceramicsmight be used in automotive applications (e.g., consoles, automotivebody parts and panels), appliances, architectural applications (e.g.,sinks, faucets, shower walls, bathtubs, outlet covers, countertops,backsplashes, elevator cabs etc.), and energy production applications(e.g., solar thermal parts).

In one or more embodiments, the glass-ceramics described herein may beincorporated into a display, and specifically as a cover for a display.In some embodiments, such glass-ceramics may be semi-opaque (i.e., havean average transmittance in the range from about 0.1% to about 25% overa wavelength range about 200 nm to about 780 nm). In such embodiments,the glass-ceramic provides a display cover that hides the light emittingdevices in the display (such as TFT displays, and backlit LED buttonsand icons) when they such light emitting devices are not in operation(i.e., the semi-opaque display cover appears completely opaque), therebyproviding a surface that does not appear to be a display (i.e., forminga “dead front”). When the light emitting devices are in operation, thelight emitting therefrom are transmitted through the semi-opaque displaycover. In one or more embodiments, such displays may be incorporatedinto countertops, cabinet doors, refrigerator doors, appliance surfaces,automotive interiors, and the like. In one or more embodiments, thedisplay cover can be touch-enabled, and thus be used to inputinformation. Such embodiments may include projected capacitive (pCAP)TFT displays, button pCAP systems and the like.

The use of glass-ceramics described herein as display covers provides animprovement over neutral density filters, which typically use thickglass materials (which may not be not suitable for high sensitivitytouch operation or for low parallax effects), or plastic (which does notprovide a durable surface). The use of glass-ceramics described here asdisplay covers also provides an improvement over semi-mirrored filmsthat are typically metallic-based and thus interfere with the electricfield of the projective capacitance touch panels resulting in little orno touch sensitivity. Moreover, the semi-mirrored films provide areflective surface when the light emitting devices are not in operation,which may be undesirable. The use of glass-ceramics described herein asdisplay covers also provides an improvement over electrochromic materialsuch as tungsten oxide and viologens (which change color when a chargeis applied and some materials can be made to transition from “clear” tosome known, repeatable dark or light state) as such electrochromicmaterials can be costly and require the use of electrodes and electricalconnections that may negatively influence the projective capacitivetouch sensors. Finally, the use of glass-ceramics described herein asdisplay covers provides an advantage over the use of micro-holes in avisually textured material, which can weaken the mechanical integrity ofthe surface, and requires a bright display to provide a sufficientlybright image to the viewer. Moreover, micro-holes are currently onlybelieved to be feasible with stainless steel materials and thus,different colors may not be achievable using this method.

Identity of phase assemblages and/or crystalline sizes for thecrystallizable glasses and glass-ceramics described herein wasdetermined or could be determined by XRD analysis techniques known tothose in the art, using such commercially available equipment as themodel as a PW1830 (Cu Kα radiation) diffractometer manufactured byPhilips, Netherlands. Spectra were typically acquired for 2θ from 5 to80 degrees.

Elemental profiles measured for characterizing the surfaces of thecrystallizable glasses and/or glass-ceramics described herein weredetermined or could be determined by analytical techniques know to thosein the art, such as, electron microprobe (EMP); x-ray photoluminescencespectroscopy (XPS); secondary ion mass spectroscopy (SIMS) . . . etc.

Compressive stress (σ_(s)) in a surface layer, average surfacecompression (CS), and depth of layer (DOL) of the crystallizable glassescan be conveniently measured using conventional optical techniques andinstrumentation such as commercially available surface stress metermodels FSM-30, FSM-60, FSM-6000LE, FSM-7000H . . . etc. available fromLuceo Co., Ltd. and/or Orihara Industrial Co., Ltd., both in Tokyo,Japan. Glass-ceramics can also be measured in a similar manner usinginfrared light sources.

During an IX processes as discussed above, ions having a smaller ionicradius present in the glass-ceramic surface and/or bulk can be exchangedwith ions having a larger ionic radius. As schematically illustrated inFIG. 5, when this results in compressive stress (σ_(s)) in the surface110 of a sample 100, balancing tensile stresses are induced in a centralregion 130 of the sample 100 to balance the forces throughout the sample100. The CS is related to the central tension (CT) by the followingrelationship:CS=CT×(t−2DOL)/DOL;

where t is the thickness of the glass-ceramic sample 100 and

-   -   DOL (depth of layer 120) is the distance from the surface 110 of        the sample 100 along a normal to the surface 110 to the location        at which the stresses within the sample 100 change sign (i.e.,        zero).

For a sample 100, the integrated central tension (ICT) is given by theintegral of stress throughout the tensile portion of the stress profile(i.e., central region 130 of the sample 100). ICT is related to the fullthickness (t) of the sample 100, the depth of layer (DOL) 120 of thecompressive stress layer, the average central tension (CT), and theshape or profile of the compressive stress layer by the followingrelationship:ICT=CT×(t−2DOL),where the thickness (t-2DOL) of the central region 130 is a directionperpendicular to the surface. To balance forces within the sample 100,the integrated surface compression (ICS) has the same magnitude as theICT, but has an opposite (minus) sign, since the overall integratedstress of the sample must be zero: −ICS+ICT=0. ICS is related to the DOL120 of the compressive stress layer, the CS, and the shape or profile ofthe compressive stress layer by the following relationship: ICS=CS×DOL,where the DOL of the compressive stress region has be defined above(i.e., the distance from the surface 110 of the sample 100 along anormal to the surface 110 to the location at which the stresses withinthe sample 100 change sign (i.e., zero)).

Vickers indentation cracking threshold measurements were performed orcould be performed on the crystallizable glasses and/or glass-ceramicsdescribed herein to identify the threshold at which cracks initiate in asurface of such materials. The measurements were performed using knowntechniques such as, for example, in pages 130-132 of “Materials Scienceand Engineering (third edition)” by William D. Callister (John Wiley &Sons, New York, 1994), which are incorporated by reference herein.Unless otherwise specified, the Vickers indentation cracking thresholdmeasurements described herein are performed by applying and thenremoving an indentation load using a Vickers indenter (a=68.00°) to aglass surface at 0.2 mm/min. The indentation maximum load is held for 10seconds. The indentation cracking threshold is defined as theindentation load at which greater than 50% of 10 indents exhibit anynumber of radial/median cracks emanating from the corners of the indentimpression. The maximum load is increased until such threshold is metfor a given glass composition. Vickers indentation cracking thresholdmeasurements are performed at room temperature in 50% relative humidity.

Flexural strength of the crystallizable glasses and/or glass-ceramicsdescribed herein was and/or can be characterized by methods know tothose in the art, such as, those described in ASTM C1499. Young'sModulus, Shear Modulus, and Poisson's Ratio of the crystallizableglasses and/or glass-ceramics described herein were and can becharacterized by methods know to those in the art, such as, thosedescribed in ASTM C1259. Knoop hardness and Vickers hardness ofcrystallizable glasses and/or glass-ceramics described herein was and/orcan be characterized by methods know to those in the art, such as, thosedescribed in ASTM C1326 and ASTM C1327, respectively.

EXAMPLES

The following examples illustrate the various embodiments of thisdisclosure and in are no way intended to limit this disclosure thereto.

Inasmuch as the sum of the individual constituents totals or veryclosely approximates 100, for all practical purposes the reported valuesmay be deemed to represent weight percent (wt %). The actualcrystallizable glass batch ingredients may comprise any materials,either oxides, or other compounds, which, when melted together with theother batch components, will be converted into the desired oxide in theproper proportions.

Example Compositions 1-115: The Example Compositions listed in Tables I,Ia, Ib and Ic were used to form crystallizable glasses by introducingappropriately batched raw materials to a platinum crucible. The cruciblewas then placed in a furnace having a temperature up to about 1700° C.The materials were then refined and the molten glasses were then eitherpoured onto a steel plate to make patties of glass, or they were formedinto sheet by rolling or down draw.

In particular, crystallizable glasses formed from Example Compositions1-7, 14-17 and 43-44 were melted by mixing 2500 g of batched rawmaterials in a 1.81 platinum crucible, which was then placed in a SiCglobar furnace having a temperature of about 1600° C. for 5 hours. Themelted materials were then poured a thin stream into a bucket of flowingcold water to make cullet. The cullet was then remelted at 1650° C. for5 hours to obtain a homogeneous melt and then poured onto a steel tableand subsequently annealed for 2 hours at about 620° C.

Example Composition 1 was formulated to evaluate the effect of highFe₂O₃ content in the composition on opacity and color. ExampleCompositions 2-6 were formulated to examine the effect of excess alkalirelative to Al₂O₃ (Na₂O+K₂O—Al₂O₃) at lower Fe₂O₃ level. This was doneto address spontaneous crystallization and improve liquidus viscosity.Example Compositions 7, 14-17 and 43-44 incorporated different levels ofTiO₂, MgO, and Fe₂O₃ to avoid magnetite, and improve the liquidusviscosity. The compositions from Example Compositions 1-7, 14-17 and43-44 that exhibited acceptable liquidus viscosities and high opacityafter ceramming, were then tuned to provide Example Compositions 53, 57,60, 63 and 71, which were made into thin sheets (having a thickness inthe range from about 1 mm to about 3 mm) on an electrically fired gasassisted continuous melting unit. The glass sheets made from ExampleCompositions 53, 57, 60, 63 and 71 were not annealed.

TABLE I Glass Composition Mole Percent (Mol %) R₂O + TiO₂ Ex. SiO₂ Al₂O₃B₂O₃ P₂O₅ Na₂O MgO CaO SnO₂ TiO₂ ZrO₂ Fe₂O₃ Co₃O₄ MnO₂ R₂O—Al₂O₃RO—Al₂O₃ Fe₂O₃ 1 63.37 13.65 5.01 0 13.48 2.33 0 0 0 0 2.16 0 0 −0.182.16 0 2 64.64 12.84 5.11 0 14.84 0.70 0 0.08 0 0 1.8 0 0 2.00 2.70 0 364.64 13.34 5.11 0 14.34 0.70 0 0.08 0 0 1.8 0 0 1.00 1.70 0 4 64.6413.84 5.11 0 13.84 0.70 0 0.08 0 0 1.8 0 0 0.00 0.70 0 5 64.64 14.345.11 0 13.34 0.70 0 0.08 0 0 1.8 0 0 −1.00 −0.30 0 6 64.64 14.84 5.11 012.84 0.70 0 0.08 0 0 1.8 0 0 −2.00 −1.30 0 7 62.64 13.84 5.11 0 13.840.70 0 0.08 2 0 1.8 0 0 0.00 0.70 1.11 8 65.22 14.97 5.16 0 12.95 0.71 00.08 0 0 0.91 0 0 −2.02 −1.31 0 9 65.03 14.93 5.14 0 12.91 0.70 0 0.08 00 1.21 0 0 −2.01 −1.31 0 10 64.83 14.88 5.12 0 12.88 0.70 0 0.08 0 01.50 0 0 −2.01 −1.30 0 11 63.02 13.92 5.14 0 13.92 0.70 0 0.08 2.01 01.21 0 0 0.00 0.70 1.67 12 61.00 14.93 5.14 0 12.91 0.70 0 0.08 4.02 01.21 0 0 −2.01 −1.31 3.33 13 58.99 14.93 5.14 0 12.91 0.70 0 0.08 6.04 01.21 0 0 −2.01 −1.31 5 14 62.64 13.93 5.11 0 13.75 2 0 0.08 2 0 0.5 0 0−0.18 1.82 4 15 63.64 13.93 5.11 0 13.75 1.75 0 0.08 1 0 0.75 0 0 −0.181.57 1.33 16 62.64 13.93 5.11 0 13.75 1.75 0 0.08 2 0 0.75 0 0 −0.181.57 2.67 17 61.64 13.93 5.11 0 13.75 1.75 0 0.08 3 0 0.75 0 0 −0.181.57 4 18 63.64 13.93 5.11 0 13.75 1.50 0 0.08 1 0 1 0 0 −0.18 1.32 1 1963.64 13.93 5.11 0 13.75 1.25 0 0.08 1 0 1.25 0 0 −0.18 1.07 0.80 2064.70 14.85 5.11 0 12.75 2 0 0.08 0 0 0.5 0 0 −2.10 −0.10 0 21 64.7014.85 5.11 0 12.75 1.75 0 0.08 0 0 0.75 0 0 −2.10 −0.35 0 22 64.70 14.855.11 0 12.75 1.50 0 0.08 0 0 1.00 0 0 −2.10 −0.60 0 23 64.54 14.81 5.100 12.72 1.75 0 0.08 0 0 0.75 0.25 0 −2.10 −0.35 0 24 64.38 14.78 5.09 012.69 1.74 0 0.08 0 0 0.75 0.5 0 −2.09 −0.35 0 25 63.20 14.85 5.11 012.75 1.75 0 0.08 1.50 0 0.75 0 0 −2.10 −0.35 2 26 63.11 14.03 5.15 013.85 1.01 0 0.08 2.01 0 0.76 0 0 −0.18 0.83 2.67 27 62.79 13.96 5.12 013.78 1.50 0 0.08 2.00 0 0.75 0 0 −0.18 1.32 2.67 28 62.48 13.89 5.10 013.71 1.99 0 0.08 1.99 0 0.75 0 0 −0.18 1.82 2.67 29 62.64 13.43 5.11 014.25 1.75 0 0.08 2 0 0.75 0 0 0.82 2.57 2.67 30 62.64 14.43 5.11 013.25 1.75 0 0.08 2 0 0.75 0 0 −1.18 0.57 2.67 31 59.80 14.95 0.00 4.9814.95 2.49 0 0.08 1.99 0 0.75 0 0 0.00 2.49 2.67 32 63.50 13.83 5.46 013.65 1.74 0 0.08 0.99 0 0.74 0 0 −0.18 1.56 1.33 33 64.20 13.25 5.12 013.75 1.75 0 0.08 1.1 0 0.75 0 0 0.50 2.25 1.47 34 63.64 13.93 5.11 013.75 1.75 0 0.08 1 0 0.75 0 0 −0.18 1.57 1.33 35 61.75 13.43 5.11 014.25 2.38 0 0.08 0 0 3 0 0 0.82 3.20 0 36 61.75 13.93 5.11 0 13.75 2.380 0.08 0 0 3 0 0 −0.18 2.20 0 37 61.75 14.43 5.11 0 13.25 2.38 0 0.08 00 3 0 0 −1.18 1.20 0 38 62.75 13.93 5.11 0 13.75 2.38 0 0.08 0 0 2 0 0−0.18 2.20 0 39 60.75 13.93 5.11 0 13.75 2.38 0 0.08 0 0 4 0 0 −0.182.20 0 40 63.75 13.93 5.11 0 13.75 2.38 0 0.08 0 1 0 0 0 −0.18 2.20 — 4163.64 13.93 5.11 0 13.75 1.75 0 0.08 1 0 0.75 0 0 −0.18 1.57 1.33 4264.62 13.44 5.11 0 13.24 1.75 0 0.08 1 0 0.75 0 0 −0.20 1.55 1.33 4364.05 13.93 5.11 0 13.75 1.75 0 0.08 0.83 0 0.50 0 0 −0.18 1.57 1.66 4463.78 13.93 5.11 0 13.75 1.75 0 0.08 1 0 0.60 0 0 −0.18 1.57 1.67 4563.51 13.93 5.11 0 13.75 1.75 0 0.08 1.17 0 0.70 0 0 −0.18 1.57 1.67 4663.65 13.90 5.10 0 13.72 1.75 0 0.08 1 0 0.60 0 0.2 −0.18 1.57 1.67 4763.53 13.87 5.09 0 13.70 1.74 0 0.08 1 0 0.60 0 0.4 −0.18 1.56 1.67 4864.18 13.93 5.11 0 13.75 1.75 0 0.08 0 0 0.60 0 0.6 −0.18 1.57 0 R₂O +TiO₂ Ex. SiO₂ Al₂O₃ B₂O₃ P₂O₅ Na₂O K₂O MgO CaO SnO₂ TiO₂ ZrO₂ Fe₂O₃Co₃O₄ MnO₂ R₂O—Al₂O₃ RO—Al₂O₃ Fe₂O₃ 49 63.77 13.92 5.12 0 13.71 0.011.92 0.04 0.09 0.98 0.02 0.42 0 0 −0.19 1.78 2.34 51 63.74 13.96 5.12 013.69 0.01 1.75 0.03 0.12 1.00 0.03 0.55 0 0.01 −0.25 1.53 1.8 52 63.7913.92 5.12 0 13.66 0.01 1.74 0.04 0.12 0.98 0.03 0.56 0 0 −0.25 1.531.74 53 63.82 13.89 5.10 0 13.76 0.01 1.74 0.03 0.06 0.98 0.03 0.56 0 0−0.11 1.67 1.73 54 53.71 13.83 5.08 0 13.76 0.02 1.75 0.03 0.05 0.980.03 0.56 0 0.19 −0.06 1.91 1.73 55 63.77 13.96 5.08 0 13.56 0.02 1.750.04 0.06 0.99 0.03 0.57 0 0.19 −0.39 1.4 1.74 56 63.81 13.83 5.08 013.61 0.01 1.75 0.03 0.05 1.2 0.03 0.57 0 0.02 −0.21 1.59 2.12 57 63.8113.69 5.11 0 13.60 0.02 1.74 0.03 0.05 1.35 0.03 0.56 0 0.01 −0.07 1.712.41 58 63.83 13.66 5.13 0 13.62 0.02 1.76 0.03 0.05 1.24 0.03 0.63 00.01 −0.03 1.77 1.98 59 63.96 13.61 5.17 0 13.63 0.01 1.75 0.03 0.061.00 0.06 0.71 0 0.01 0.03 1.82 1.42 60 63.94 13.60 5.18 0 13.66 0.011.75 0.03 0.06 0.99 0.06 0.71 0 0.01 0.08 1.87 1.40 61 64.05 13.6 5.17 013.77 0.01 1.43 0.03 0.05 0.98 0.06 0.74 0 0.11 0.18 1.64 1.33 62 64.2313.58 5.19 0 13.70 0.02 1.22 0.03 0.05 0.98 0.07 0.75 0 0.19 0.14 1.581.30 63 65.08 13.19 4.97 0 13018 0.01 1.73 0.03 0.03 0.98 0.04 0.75 00.01 0 1.77 1.32 64 65.06 13.13 5.03 0 13.22 0.01 1.75 0.03 0.02 0.980.02 0.74 0 0.01 0.1 1.89 1.32 65 64.91 13.13 5.15 0 13.11 0.01 1.730.03 0.02 0.97 0.02 0.63 0.26 0.01 0 1.77 1.54 66 65.16 13.31 4.85 012.16 0.95 1.74 0.04 0.02 0.99 0.02 0.75 0.01 0.01 −0.2 1.58 1.32 6765.46 12.95 4.50 0 13.04 0.39 1.54 0.03 0.02 1.30 0.01 0.74 0.01 0.010.48 2.06 1.76 68 66.00 12.70 3.74 0 13.60 0.04 1.62 0.03 0.02 1.47 0.010.76 0.01 0.01 0.94 2.6 1.93 69 65.97 12.77 3.68 0 13.62 0.02 1.41 0.030.02 1.49 0.01 0.76 0.01 0.22 0.87 2.52 1.95 70 65.96 12.70 3.71 0 12.790.88 1.61 0.03 0.02 1.50 0.01 0.76 0.01 0.03 0.97 2.63 1.96 71 66.1312.73 3.69 0 13.17 0.55 1.63 0.03 0.02 1.32 0.01 0.68 0.01 0.03 0.992.67 1.95

TABLE Ia Glass Composition Mole Percent (Mol %) R₂O + TiO₂ Ex. SiO₂Al₂O₃ P₂O₅ Na₂O K₂O MgO CaO SrO BaO ZnO La₂O₃ Ta₂O₅ SnO₂ TiO₂ Fe₂O₃R₂O—Al₂O₃ RO—Al₂O₃ Fe₂O₃ 72 60.15 14.98 5 14.98 0 2.49 0.06 0 0 0 0 00.08 1.50 0.75 0 2.56 2 74 60.89 14.99 4.99 14.98 0 2.51 0.06 0 0 0 0 00.08 0.75 0.75 0 2.57 1 75 61.14 14.98 5 14.98 0 2.51 0.06 0 0 0 0 00.08 0.5 0.75 0 2.57 0.67 76 60.42 14.98 4.99 14.98 0 2.49 0.06 0 0 0 00 0.08 2 0.00 0 2.55 — 78 60.30 15.02 5.01 15.01 0 2.50 0.06 0 0 0 0 00.08 1.50 0.50 −0.01 2.56 2.99 79 60.23 15.01 5 15.00 0 2.51 0.06 0 0 00 0 0.08 1.51 0.60 −0.01 2.56 2.50 80 60.00 14.95 4.98 14.95 0 2.48 0.060 0 0 0 0 0.08 1.50 1.00 0 2.55 1.50 81 60.30 15.02 5.01 15.03 0 2.010.05 0 0 0 0 0 0.08 1.50 1.00 0 2.07 1.50 82 60.91 15.18 5.06 15.18 01.02 0.05 0 0 0 0 0 0.08 1.51 1.01 0 1.08 1.50 83 60.37 14.99 5 14.99 02.49 0.06 0 0 0 0 0 0.08 0 2 0 2.56 0 84 57.08 15.56 7.55 15.09 0.470.38 3.78 0 0 0 0 0 0.08 0 0 0.01 4.16 0 86 55.01 15.00 10.91 14.55 0.460.36 3.64 0 0 0 0 0 0.08 0 0 0.01 4.00 0 87 56.02 15.28 11.11 14.81 0.460.38 1.85 0 0 0 0 0 0.08 0 0 0 2.23 0 90 57.07 15.57 8.49 15.11 0.470.38 2.83 0 0 0 0 0 0.07 0 0 0.01 3.23 — 91 57.08 15.57 8.49 15.11 0.470.37 0.00 0 0 2.83 0 0 0.07 0 0 0.01 3.21 — 92 57.09 15.57 8.49 15.090.47 0.37 0.00 2.83 0 0 0 0 0.07 0 0 −0.01 3.19 — 93 57.08 15.57 8.4915.10 0.47 0.38 0.00 0 2.83 0 0 0 0.08 0 0 0 3.22 — 94 57.07 15.57 8.4915.10 0.48 0.38 0.00 0 0 0 2.83 0 0.08 0 0 0.01 0.39 — 95 57.10 15.578.49 15.09 0.47 0.38 0.00 0 0 0 0 2.83 0.07 0 0 −0.01 0.37 — 96 56.0215.27 5.56 14.83 0.47 0.38 3.70 0 0 0 0 0 0.08 3.71 0 0.02 4.09 — 9755.02 15.00 7.28 14.54 0.45 0.36 3.63 0 0 0 0 0 0.07 3.63 0 −0.01 3.99 —98 54.03 14.74 8.93 14.29 0.44 0.35 3.57 0 0 0 0 0 0.07 3.57 0 0 3.92 —99 56.04 15.28 7.41 14.81 0.46 0.37 1.85 0 0 0 0 0 0.07 3.70 0 −0.012.21 — 100 55.00 14.55 7.27 15.00 0.46 0.36 3.64 0 0 0 0 0 0.07 3.63 00.91 4.91 — 101 55.01 15.46 7.27 14.09 0.45 0.36 3.64 0 0 0 0 0 0.073.63 0 −0.92 3.09 — 102 59.91 16.34 5.94 15.84 0.50 0.39 0.99 0 0 0 0 00.08 0 0 0 1.38 — 103 59.33 16.18 5.88 15.69 0.49 0.39 1.97 0 0 0 0 00.08 0 0 0 2.36 — 104 58.17 15.87 5.77 15.39 0.48 0.39 3.85 0 0 0 0 00.08 0 0 0 4.24 — 105 58.18 15.87 7.69 15.39 0.48 0.38 1.92 0 0 0 0 00.08 0 0 0 2.31 — 106 59.32 15.69 5.89 16.18 0.49 0.39 1.96 0 0 0 0 00.08 0 0 0.98 3.33 — 107 59.32 16.67 5.88 15.21 0.49 0.39 1.96 0 0 0 0 00.08 0 0 −0.97 1.38 —

TABLE Ib Glass Composition Mole Percent (Mol %) R₂O + TiO₂ Ex. SiO₂Al₂O₃ B₂O₃ Na₂O MgO TiO₂ Fe₂O₃ CuO Cu2O R₂O—Al₂O₃ RO—Al₂O₃ Fe₂O₃ 108 6513.2 5 13.3 1.75 1 0.75 0 0 0.1 1.85 1.33 109 65 13.2 5 13.2 1.75 1 0.750.2 0 0 1.95 1.33 110 65 13.2 5 12.3 1.75 1 0.75 2 0 −0.9 2.85 1.33 11165 13.2 5 8.3 1.75 1 0.75 10 0 −4.9 6.85 1.33 112 65 13.2 5 8.3 1.75 10.75 0 5 0.1 1.85 1.33 113 65 13.2 5 13.3 1.75 0 0 0.2 0 0.1 2.8 0

TABLE Ic Glass Composition Mole Percent (Mol %) R₂O + TiO₂ Ex. SiO₂Al₂O₃ B₂O₃ Na₂O K₂O MgO CaO SnO2 ZrO2 TiO2 Fe2O3 MnO CoO R₂O—Al₂O₃RO—Al₂O₃ Fe₂O₃ 114 63.803 13.989 5.098 13.655 0.014 1.747 0.034 0.0600.028 0.986 0.581 0.00 0.00 −0.320 1.461 1.697 115 64.919 13.189 5.06013.163 0.014 1.751 0.031 0.020 0.020 0.983 0.677 0.00 0.17 −0.011 1.7711.452

TABLE II Glass Properties Heat Treated Glass Strain Annealing Softeningα P T_(lqds) LiqVisc Liquidus PB Crystal Ex. Point (° C.) Point (° C.)Point (° C.) (10⁻⁷/° C.) (g/cm³) (° C.) (kP) Phase(s) As Made 700° C.-4hr 750° C.-4 hr 800° C.-4 hr Size (nm) 1 559 608 888 76.1 2.46 1235 12.2Mag Mag Mag Mag 2 Mag Amorph Amorph Amorph 3 1050 402 <1050° C. AmorphMag Mag 4 Hem + Ma Amorph Mag Mag 5 Hem + Ma Mag Mag Mag 6 Hem + MaMag + Hem Mag + Hem Mag 7 PB Mag Mag + PB Mag + PB 8 Amorph AmorphAmorph 9 Amorph Mag + Hem Mag + Hem 10 Amorph Mag Mag 11 Mag + possiblyMag + PB another phase 12 PB + possibly PB another phase 13 PB + RutilePB + Rutile 14 566 617 900 2.43 1110 116 Amorph PB PB 15 560 612 8832.42 1050 493 Amorph ε-Fe₂O₃ ε-Fe₂O₃ 16 563 613 891 2.43 1140 60 AmorphMag + PB PB 17 566 619 904 2.45 1155 <45 Amorph PB PB 18 556 607 8802.43 Amorph Mag Mag + PB 19 559 609 893 2.43 Amorph Mag Mag + possiblyanother phase 20 21 22 23 24 25 26 574 626 2.43 1120 PB PB 18 27 572 6262.43 1110 trace Mag PB 17 18 570 623 2.44 1105 PB PB 17 29 559 608 2.441085 PB PB 20 30 575 627 2.43 1135 PB PB 15 31 625 680 2.45 1065 658 321045 470 33 1050 34 1065 35 36 37 38 39 40 41 2.42 1095 216 42 2.42 1070422 43 1065 Amorph ε-Fe₂O₃ ε-Fe₂O₃ 44 1070 Amorph ε-Fe₂O₃ ε-Fe₂O₃ 451100 46 1060 47 1065 48 1030 Glass Properties Strain Pt. AnnealingSoftening α P Beta- T_(lqds) (° C.)-24 hrs T_(lqds) (° C.)-72 hrsLiqVisc (Kp)-24 hr LiqVisc (Kp)-72 hr HTV Ex. (° C.) Pt. (° C.) Pt. (°C.) (10⁻⁷/° C.) (g/cm³) OH Air Int. Pt. Air Int. Pt. Air Int. Pt. AirInt. Pt. A B To 49 1070 1065 1080 −3.6 9581.7 30.1 51 567 619 2.4090.405 −3.5 9092.2 59.7 52 53 2.407 1075 1025 1040 335 1010 1040 335 967696 274 1358 696 −3.5 9256.3 40.0 54 55 1075 1035 1055 311 311 726 47156 565 617 881.9 74.1 2.408 0.391 −3.4 8983.9 57.7 57 1095 1045 1085 181181 496 220 58 −3.9 10198.7 −32.1 59 −3.5 9403.4 41.9 60 562 613 2.3530.373 1100 1035 1075 170 170 637 277 −3.2 8610.6 86.9 61 559 611 74.72.412 0.365 −3.8 10189.2 −12.7 62 1125 1075 1040 90 90 224 448 −3.59439.9 31.6 63 1120 1050 1055 150 1055 1075 150 604 544 125 544 359 −3.39104.4 53.6 64 1025 1050 136 950 549 −3.5 9573.9 29.4 65 1020 1015 2081066 1191 −3.4 9383.4 33.6 66 1045 1110 132 692 190 −3.3 9156.8 45.9 671045 1090 159 702 280 −3.9 10646.2 −46.7 68 1125 1150 62 161 103 69 567617 2.418 0.358 1040 1085 183 811 323 −3.3 8945.3 54.1 70 1050 1075 138650 391 −3.9 10557.8 −43.7 71 1015 1015 1040 1349 1349 793 −3.6 9581.730.1 Glass Properties Heat Treated Glass Ex. T200 P T16 kP T35 kP T160kP 700° C.-4 hr 750° C.-4 hr 800° C.-4 hr PB Crystal Size (nm) 49 51 5253 1641 1251 1200 1113 ε-Fe₂O₃ ε-Fe₂O₃ ε-Fe₂O₃ 54 55 1637 1246 1195 110956 57 1632 1239 1189 1102 PB PB 58 59 60 1637 1241 1190 1103 ε-Fe₂O₃ 6162 1623 1232 1181 1093 63 1650 1255 1204 1116 ε-Fe₂O₃ ε-Fe₂O₃ 64 16521250 1199 1111 65 1647 1254 1203 1114 66 1666 1261 1209 1119 67 16691261 1209 1120 68 1671 1267 1215 1125 69 1675 1265 1213 1122 70 16791265 1212 1122 71 1671 1267 1214 1123 ε-Fe₂O₃ ε-Fe₂O₃ PB + ε-Fe₂O₃ GlassProperties Heat Treated Glass Ex. Annealing Pt (° C.) P (g/cm³) T_(lqds)(° C.) Color (850° C.-4 hr) XRD (750° C.-4 hr) XRD (780° C.-4 hr) XRD(800° C.-4 hr) XRD (850° C.-4 hr) 72 700 Brown Rutile, PB, Hematite 74700 Amber translucent Amorphous 75 700 Amber translucent Amorphous 76700 White GC Anatase 78 680 Khaki Grey translucent Trace Berlinite,Magnetite Trace Rutile Rutile 79 680 Khaki Grey translucent TraceBerlinite, Magnetite Rutile Rutile 80 680 Black Opaque PB, Berlinite,Magnetite PB, Rutile PB, Rutile 81 680 1080 Black Opaque PB, Berlinite,Magnetite PB, Rutile PB, Rutile 82 680 1090 Black Opaque PB, Berlinite,Magnetite PB, Rutile PB, Rutile 83 680 Black Opaque Magnetite orMagnetite or Magnetite or Magnesioferrite MagnesioferriteMagnesioferrite 84 680 White Light Opal 86 680 White Opal 87 680 ClearGlass Amorphous Amorphous Amorphous Amorphous 90 680 White Opal 91 680Clear Glass 92 680 White Opal 93 680 Clear Glass 94 680 SpontaneousCeramic 95 680 Clear Glass 96 680 Bluish White Light Opal 97 680 WhiteGC 98 680 Cream Opal 99 680 White GC 100 680 White GC 101 680 White Opal102 680 103 680 104 680 105 680 106 680 107 680

TABLE III Example-> 49 51 52 53 XRD Results As Made Glass amorphous HeatTreated Glasses Nucleation Growth Temperature-time Temperature-(T_(n)-t_(n)) time (T_(c)-t_(c)) 630° C.-2 hrs 675° C.-4 hrs 630° C.-2hrs 700° C.-4 hrs 630° C.-2 hrs 725° C.-4 hrs Amorphous 630° C.-2 hrs750° C.-4 hrs ε-Fe₂O₃ 630° C.-2 hrs 775° C.-4 hrs ε-Fe₂O₃ 630° C.-2 hrs800° C.-4 hrs ε-Fe₂O₃ Indentation Threshold (kg) As Made Glass-> 37.5Heat Treated Glasses Tn-tn Tc-tc 630° C.-2 hrs 675° C.-4 hrs 50 630°C.-2 hrs 700° C.-4 hrs 22.5 630° C.-2 hrs 725° C.-4 hrs 630° C.-2 hrs750° C.-4 hrs Transmission Percent (%) As Made Glass-> Heat TreatedGlasses Tn-t_(n) Tc-t_(c) 630° C.-2 hrs 675° C.-4 hrs 13.22 27.98 630°C.-2 hrs 700° C.-4 hrs 83.49 0.98 0.97 630° C.-2 hrs 725° C.-4 hrs 0.07na 630° C.-2 hrs 750° C.-4 hrs 0.08 0.05 630° C.-2 hrs 775° C.-4 hrs 4630° C.-2 hrs 800° C.-4 hrs na Example−> 54 55 56 57 58 XRD Results AsMade Glass Heat Treated Glasses Nucleation Growth Temperature-timeTemperature- (T_(n)-t_(n)) time (T_(c)-t_(c)) 630° C.-2 hrs 675° C.-4hrs 630° C.-2 hrs 700° C.-4 hrs 630° C.-2 hrs 725° C.-4 hrs ε-Fe₂O₃ 630°C.-2 hrs 750° C.-4 hrs ε-Fe₂O₃ PB ε-Fe₂O₃ 630° C.-2 hrs 775° C.-4 hrsε-Fe₂O₃ PB 630° C.-2 hrs 800° C.-4 hrs ε-Fe₂O₃ Indentation Threshold(kg) As Made Glass-> 37.5 Heat Treated Glasses Tn-tn Tc-tc 630° C.-2 hrs675° C.-4 hrs 22.5 630° C.-2 hrs 700° C.-4 hrs 630° C.-2 hrs 725° C.-4hrs 630° C.-2 hrs 750° C.-4 hrs Transmission Percent (%) As Made Glass->Heat Treated Glasses Tn-t_(n) Tc-t_(c) 630° C.-2 hrs 675° C.-4 hrs 3.710.06 0.07 0.08 630° C.-2 hrs 700° C.-4 hrs 0.08 0.16 0.06 0.08 0.06 630°C.-2 hrs 725° C.-4 hrs 0.09 0.08 0.11 0.09 630° C.-2 hrs 750° C.-4 hrs0.04 0.04 0.15 0.63 0.08 630° C.-2 hrs 775° C.-4 hrs 0.13 0.95 630° C.-2hrs 800° C.-4 hrs Example-> 59 60 61 62 63 XRD Results As Made GlassAmorphous Amorphous Heat Treated Glasses Nucleation GrowthTemperature-time Temperature- (T_(n)-t_(n)) time (T_(c)-t_(c)) 630° C.-2hrs 675° C.-4 hrs 630° C.-2 hrs 700° C.-4 hrs ε-Fe₂O₃ ε-Fe₂O₃ 630° C.-2hrs 725° C.-4 hrs ε-Fe₂O₃ Trace Magnetite 630° C.-2 hrs 750° C.-4 hrsε-Fe₂O₃ ε-Fe₂O₃ ε-Fe₂O₃ ε-Fe₂O₃ 630° C.-2 hrs 775° C.-4 hrs ε-Fe₂O₃ε-Fe₂O₃ ε-Fe₂O₃ 630° C.-2 hrs 800° C.-4 hrs Indentation Threshold (kg)As Made Glass-> Heat Treated Glasses Tn-tn Tc-tc 630° C.-2 hrs 675° C.-4hrs 630° C.-2 hrs 700° C.-4 hrs 630° C.-2 hrs 725° C.-4 hrs 630° C.-2hrs 750° C.-4 hrs Transmission Percent (%) As Made Glass-> Heat TreatedGlasses Tn-t_(n) Tc-T_(c) 630° C.-2 hrs 675° C.-4 hrs 0.06 630° C.-2 hrs700° C.-4 hrs 0.07 0.86 0.08 0.03 630° C.-2 hrs 725° C.-4 hrs 0.05 0.030.07 0.04 0.03 630° C.-2 hrs 750° C.-4 hrs 0.07 0.02 0.07 0.03 630° C.-2hrs 775° C.-4 hrs 0.03 0.05 630° C.-2 hrs 800° C.-4 hrs Example-> 64 6566 67 68 XRD Results As Made Glass Heat Treated Glasses NucleationGrowth Temperature-time Temperature- (T_(n)-t_(n)) time (T_(c)-t_(c))630° C.-2 hrs 675° C.-4 hrs 630° C.-2 hrs 700° C.-4 hrs 630° C.-2 hrs725° C.-4 hrs 630° C.-2 hrs 750° C.-4 hrs PB 630° C.-2 hrs 775° C.-4 hrsPB 630° C.-2 hrs 800° C.-4 hrs Indentation Threshold (kg) As MadeGlass-> Heat Treated Glasses Tn-tn Tc-tc 630° C.-2 hrs 675° C.-4 hrs630° C.-2 hrs 700° C.-4 hrs 17.5 630° C.-2 hrs 725° C.-4 hrs 630° C.-2hrs 750° C.-4 hrs Transmission Percent (%) As Made Glass-> Heat TreatedGlasses Tn-t_(n) Tc-t_(c) 630° C.-2 hrs 675° C.-4 hrs 0.09 0.04 0.020.05 630° C.-2 hrs 700° C.-4 hrs 0.09 0.03 0.02 0.03 630° C.-2 hrs 725°C.-4 hrs 0.02 0.03 0.05 0.02 0.02 630° C.-2 hrs 750° C.-4 hrs 0.03 0.020.03 0.03 0.03 630° C.-2 hrs 775° C.-4 hrs 0.03 0.02 0.05 0.92 1.35 630°C.-2 hrs 800° C.-4 hrs Example-> 69 70 71 XRD Results As Made GlassAmorphous Heat Treated Glasses Nucleation Growth Temperature-timeTemperature- (T_(n)-t_(n)) time (T_(c)-t_(c)) 630° C.-2 hrs 675° C.-4hrs 630° C.-2 hrs 700° C.-4 hrs 630° C.-2 hrs 725° C.-4 hrs 630° C.-2hrs 750° C.-4 hrs 630° C.-2 hrs 775° C.-4 hrs 630° C.-2 hrs 800° C.-4hrs Indentation Threshold (kg) As Made Glass-> 35-40 Heat TreatedGlasses Tn-tn Tc-tc 630° C.-2 hrs 675° C.-4 hrs 630° C.-2 hrs 700° C.-4hrs 37.5 630° C.-2 hrs 725° C.-4 hrs 630° C.-2 hrs 750° C.-4 hrsTransmission Percent (%) As Made Glass-> Heat Treated Glasses Tn-t_(n)Tc-t_(c) 630° C.-2 hrs 675° C.-4 hrs 0.02 0.03 0.02 630° C.-2 hrs 700°C.-4 hrs 0.02 0.03 0.02 630° C.-2 hrs 725° C.-4 hrs 0.02 0.03 0.03 630°C.-2 hrs 750° C.-4 hrs 0.04 0.04 0.04 630° C.-2 hrs 775° C.-4 hrs 0.4 0.97 0.25 630° C.-2 hrs 800° C.-4 hrs

TABLE IV Example-> 49 51 52 53 CIE L* D65 SCE Results As Made Glass HeatTreated Glasses Nucleation Growth Temperature- Temperature- time(T_(n)-t_(n)) time (T_(c)-t_(c)) 630° C.-2 hrs 675° C.-4 hrs 0.54 2.78630° C.-2 hrs 700° C.-4 hrs 64.69 0.28 0.25 630° C.-2 hrs 725° C.-4 hrs0.93 0.6 630° C.-2 hrs 750° C.-4 hrs 3.2 5.67 630° C.-2 hrs 775° C.-4hrs 17.085 10.21 630° C.-2 hrs 800° C.-4 hrs 26.76 CIE a* D65 SCEResults As Made Glass-> Heat Treated Glasses Tn-tn Tc-tc 630° C.-2 hrs675° C.-4 hrs 0.62 7.09 630° C.-2 hrs 700° C.-4 hrs 2.6 0.05 0.03 630°C.-2 hrs 725° C.-4 hrs −0.1 0.08 630° C.-2 hrs 750° C.-4 hrs −0.3 −0.135630° C.-2 hrs 775° C.-4 hrs −1.15 −0.54 630° C.-2 hrs 800° C.-4 hrs−1.29 CIE b* D65 SCE Results As Made Glass-> Heat Treated GlassesTn-t_(n) Tc-t_(c) 630° C.-2 hrs 675° C.-4 hrs −0.14 3.59 630° C.-2 hrs700° C.-4 hrs 28.68 −0.31 −0.35 630° C.-2 hrs 725° C.-4 hrs −1.46 −0.95630° C.-2 hrs 750° C.-4 hrs −3.75 −4.89 630° C.-2 hrs 775° C.-4 hrs−6.265 −6.06 630° C.-2 hrs 800° C.-4 hrs −2.82 Example-> 54 55 56 57 58CIE L* D65 SCE Results As Made Glass Heat Treated Glasses NucleationGrowth Temperature- Temperature- time (T_(n)-t_(n)) time (T_(c)-t_(c))630° C.-2 hrs 675° C.-4 hrs 0.39 0.26 0.19 0.41 630° C.-2 hrs 700° C.-4hrs 0.345 0.27 0.27 0.2 630° C.-2 hrs 725° C.-4 hrs 1.14 0.29 0.22 0.19630° C.-2 hrs 750° C.-4 hrs 2.08 0.29 0.34 0.35 630° C.-2 hrs 775° C.-4hrs 0.99 1.28 630° C.-2 hrs 800° C.-4 hrs CIE a* D65 SCE Results As MadeGlass-> Heat Treated Glasses Tn-tn Tc-tc 630° C.-2 hrs 675° C.-4 hrs−0.03 0.03 0.01 0.04 630° C.-2 hrs 700° C.-4 hrs 0.005 −0.08 0 −0.01630° C.-2 hrs 725° C.-4his −0.12 −0.15 −0.04 0.04 630° C.-2 hrs 750°C.-4 hrs −0.21 0.07 −0.06 −0.06 630° C.-2 hrs 775° C.-4 hrs −0.09 −0.09630° C.-2 hrs 800° C.-4 hrs CIE b* D65 SCE Results As Made Glass-> HeatTreated Glasses Tt-t_(n) Tc-t_(c) 630° C.-2 hrs 675° C.-4 hrs −0.48−0.41 −0.25 −0.53 630° C.-2 hrs 700° C.-4 hrs −0.74 −0.34 −0.36 −0.26630° C.-2 hrs 725° C.-4 hrs −1.62 −0.36 −0.29 −0.3 630° C.-2 hrs 750°C.-4 hrs −2.53 −0.41 −0.55 −0.44 630° C.-2 hrs 775° C.-4 hrs −1.25 −1.89630° C.-2 hrs 800° C.-4 hrs Example-> 59 60 61 62 63 CIE L* D65 SCEResults As Made Glass Heat Treated Glasses Nucleation GrowthTemperature- Temperature- time (T_(n)-t_(n)) time (T_(c)-t_(c)) 630°C.-2 hrs 675° C.-4 hrs 0.24 630° C.-2 hrs 700° C.-4 hrs 0.17 0.45 0.330.18 630° C.-2 hrs 725° C.-4 hrs 0.5 0.23 0.26 0.2 0.12 630° C.-2 hrs750° C.-4 hrs 0.7 1.37 0.77 0.45 630° C.-2 hrs 775° C.-4 hrs 1.09 0.56630° C.-2 hrs 800° C.-4 hrs CIE a* D65 SCE Results As Made Glass-> HeatTreated Glasses Tn-tn Tc-tc 630° C.-2 hrs 675° C.-4 hrs −0.01 630° C.-2hrs 700° C.-4 hrs 0.02 0.11 0.02 −0.05 630° C.-2 hrs 725° C.-4 hrs −0.010.03 −0.01 0.065 0.03 630° C.-2 hrs 750° C.-4 hrs −0.05 0.15 −0.07 0.02630° C.-2 hrs 775° C.-4 hrs 0.07 −0.05 630° C.-2 hrs 800° C.-4 hrs CIEb* D65 SCE Results As Made Glass-> Heat Treated Glasses Tt-t_(n)Tc-t_(c) 630° C.-2 hrs 675° C.-4 hrs −0.42 630° C.-2 hrs 700° C.-4 hrs−0.28 −0.43 −0.39 −0.27 630° C.-2 hrs 725° C.-4 hrs −0.91 −0.33 −0.4−0.295 −0.19 630° C.-2 hrs 750° C.-4 hrs −1.06 −0.25 −0.9 −0.26 630°C.-2 hrs 775° C.-4 hrs −1.29 −0.74 630° C.-2 hrs 800° C.-4 hrs Example->64 65 66 67 68 CIE L* D65 SCE Results As Made Glass Heat Treated GlassesNucleation Growth Temperature- Temperature- time (T_(n)-t_(n)) time(T_(c)-t_(c)) 630° C.-2 hrs 675° C.-4 hrs 0.29 0.16 0.19 630° C.-2 hrs700° C.-4 hrs 0.5 0.19 0.2 0.24 630° C.-2 hrs 725° C.-4 hrs 0.37 0.290.45 0.24 0.47 630° C.-2 hrs 750° C.-4 hrs 0.3 0.25 0.31 0.4 0.51 630°C.-2 hrs 775° C.-4 hrs 0.72 0.48 0.43 4.24 3.8 630° C.-2 hrs 800° C.-4hrs CIE a* D65 SCE Results As Made Glass-> Heat Treated Glasses Tn-tnTc-tc 630° C.-2 hrs 675° C.-4 hrs −0.08 0.08 −0.02 630° C.-2 hrs 700°C.-4 hrs −0.11 0.04 −0.09 0 630° C.-2 hrs 725° C.-4 hrs −0.06 0.01 0.04−0.02 0.03 630° C.-2 hrs 750° C.-4 hrs −0.05 −0.06 −0.07 0.03 0.07 630°C.-2 hrs 775° C.-4 hrs −0.08 −0.04 −0.01 −0.61 −0.55 630° C.-2 hrs 800°C.-4 hrs CIE b* D65 SCE Results As Made Glass-> Heat Treated GlassesTn-t_(n) Tc-t_(c) 630° C.-2 hrs 675° C.-4 hrs −0.37 −0.41 −0.29 630°C.-2 hrs 700° C.-4 hrs −0.45 −0.4 −0.34 −0.32 630° C.-2 hrs 725° C.-4hrs −0.61 −0.31 −0.41 −0.45 −0.45 630° C.-2 hrs 750° C.-4 hrs −0.5 −0.35−0.25 −0.62 −0.88 630° C.-2 hrs 775° C.-4 hrs −1.03 −0.76 −0.74 −4.41−3.93 630° C.-2 hrs 800° C.-4 hrs Example-> 69 70 71 CIE L* D65 SCEResults As Made Glass Heat Treated Glasses Nucleation GrowthTemperature- Temperature- time (T_(n)-t_(n)) time (T_(c)-t_(c)) 630°C.-2 hrs 675° C.-4 hrs 0.28 0.27 0.2 630° C.-2 hrs 700° C.-4 hrs 0.190.15 0.21 630° C.-2 hrs 725° C.-4 hrs 0.25 0.22 1.18 630° C.-2 hrs 750°C.-4 hrs 0.39 0.49 2.04 630° C.-2 hrs 775° C.-4 hrs 3.43 4.38 4.72 630°C.-2 hrs 800° C.-4 hrs CIE a* D65 SCE Results As Made Glass-> HeatTreated Glasses Tn-tn Tc-tc 630° C.-2 hrs 675° C.-4 hrs 0.03 0.11 0.12630° C.-2 hrs 700° C.-4 hrs 0.04 0.07 0.09 630° C.-2 hrs 725° C.-4 hrs0.1 0.09 0 630° C.-2 hrs 750° C.-4 hrs 0.12 0.05 −0.01 630° C.-2 hrs775° C.-4 hrs −0.43 −0.7 −0.13 630° C.-2 hrs 800° C.-4 hrs CIE b* D65SCE Results As Made Glass-> Heat Treated Glasses Tn-t_(n) Tc-t_(c) 630°C.-2 hrs 675° C.-4 hrs −0.36 −0.34 −0.22 630° C.-2 hrs 700° C.-4 hrs−0.37 −0.33 −0.34 630° C.-2 hrs 725° C.-4 hrs −0.4 −0.33 −1.66 630° C.-2hrs 750° C.-4 hrs −0.84 −1.02 −2.67 630° C.-2 hrs 775° C.-4 hrs −3.11−4.36 −5.29 630° C.-2 hrs 800° C.-4 hrs

TABLE V Heat IOX IOX Time thickness CS DOL Ex treat Temp (hrs.) (mm)(MPa) (um) 53 630-2 430 14 0.75 949.3 50.9 57 630-2 430 14 0.76 957.949.8 59 630-2 430 14 0.76 941.3 49.8 — 630-1 430 14 0.77 952.6 48.9 61630-2 430 14 0.74 915.1 48.5 66 630-2 430 14 0.78 859.8 37.8 68 71 630-2430 14 0.76 938.3 56.2 53 630-2 410 8 0.75 1012.2 31.8 57 630-2 410 80.78 1024.7 28.4 59 — 630-2 410 8 0.79 1046.9 29.7 61 630-2 410 8 0.75990.1 30.3 66 68 630-1 410 8 0.79 1053.4 30.4 71 630-2 410 8

Tables II-IV show various properties of the crystallizable glasses andglass-ceramics formed from the Example Compositions in Table I. In TableII, reference to “Amorph” refers to amorphous, “Fay” refers to Fayalite,“Hem” refers to Hematite, “PB” refers to pseudobrookite, and “Mag”refers to Magnetite. Also in Table II, reference to α (10⁻⁷/° C.) refersto the coefficient of thermal expansion. Table V includes some heattreatment conditions and IOX conditions, and CS/DOL measurements usingFSM, for selected crystallizable glasses, just after nucleation. FSMmeasurements were used at this stage due to the transparency of thecrystallizable glasses. Glass-ceramics exhibit an opacity that does notpermit the visible light transmission required for FSM measurements.

The Example Compositions 1-7, 14-17, 43-44, 53, 57, 60, 63 and 71 meltedto defect-free fluid homogeneous liquids. All of Example Compositions1-7, 14-17, 43-44, 53, 57, 60, 63 and 71 formed dark amber coloredglasses that were transparent, except for Example Compositions 1 and 5-7which were black and opaque after annealing. All of the resultingglass-ceramics made from Example Compositions 1-7, 14-17, 43-44, 53, 57,60, 63 and 71, except for the glass-ceramics made from ExampleComposition 2, were black and opaque or nearly opaque. The glass-ceramicmade from Example Composition 2 exhibited no visual change afterceramming and remained transparent. FIG. 1 compares the transmissionspectra for visible and IR wavelengths obtained for as-made and heattreated glasses of Example Composition 15 and indicates the as-madeglass transmits sufficiently to enable efficient melting.

The viscosity of selected Example Compositions from Table 1 was measuredby beam bending, disk compression, and rotating cylinder methodsaccording to ASTM standards C1350M-96, C1351M-96, and C965-96respectively to cover the entire range from strain point to 10 Pa*s. Theliquidus was measured by 72 hour gradient boat, density by Archimedes,and thermal expansion by dilatometer according to ASTM standards. FIG. 4shows the viscosity versus temperature curve denoting the liquidustemperature and viscosity for the glass of Example 15.

Glasses made from selected Example Compositions were then cut intopieces for forming glass-ceramics. The glasses were heated at 5° C./minto 630° C. for 2 hours to nucleate the glass, and then heated to thefinal growth temperature, held for 4 hours, and cooled to roomtemperature at furnace rate, resulting in glass-ceramics. Since allsamples were nucleated at 630° C. for 2 hours, it is to be assumed allglass-ceramics were first nucleated at 630° C. unless otherwisespecified; hence the heat treatment nomenclature “750-4” corresponds toa sample nucleated at 630° C. for 2 hours with a final ceram hold at750° C. for 4 hours and the heat treatment nomenclature “700-4”corresponds to a sample nucleated at 630° C. for 2 hours with a finalceram hold at 700° C. for 4 hours, etc.

Glasses formed from Example Compositions 2-4, 14-17, 43-44, 53, 57, 60,63 and 71 were amorphous after annealing. Glasses formed from ExampleCompositions 1 and 5-6 exhibited magnetite peaks and Glass 7 exhibitedmagnetite and ε-Fe₂O₃. FIG. 7 shows exemplary x-ray diffraction patternsfor the 4 types of patterns observed: amorphous, ε-Fe₂O₃, (JCPDS00-016-0653), pseudobrookite (JCPDS 00-041-1432), and magnetite (JCPDS01-076-2948). Curve “a” in FIG. 7 shows the pattern for a glass-ceramicmade from Example Composition 3 after being heat treated at 750-4, whichexhibits peaks matching magnetite. Small pieces (<1 mm) of this could bepicked up by a magnet as could all the compositions which exhibited amagnetite diffraction pattern. Curve “b” in FIG. 7 shows the pattern fora glass-ceramic made from Example Composition 16 after being heattreated at 750-4. Curve “c” in FIG. 7 shows the pattern for aglass-ceramic made from Example Composition 53 after being heat treatedat 750-4. Curve “d” in FIG. 7 shows the pattern for a glass made fromExample 16 after annealing. The intensity of the magnetite peaks in theglass-ceramics increased from Example Composition 3 to ExampleComposition 6, as did the size of the glass-ceramic particles that stuckto the magnet. The glasses/glass-ceramics exhibiting pseudobrookite andε-Fe₂O₃ did not stick to a magnet even for pieces <0.1 mm. As shown inFIG. 7, the glass formed from Example Composition 16 was amorphous afterannealing but exhibited peaks corresponding to pseudobrookite afterceramming, as shown by curve “b”. Example Composition 53 expressedε-Fe₂O₃ peaks when cerammed at 750° C. as shown by curve c in FIG. 7 andeven fainter ε-Fe₂O₃ peaks when cerammed at 700° C.

FIG. 2 shows the X-ray diffraction (XRD) pattern obtained for aglass-ceramic made from Example Composition 3, after heat treating at700° C. for 4 hours, illustrating the presence of Magnetite (Fe₃O₄).FIG. 3 shows the XRD pattern obtained for a glass-ceramic made fromExample Composition 16, after heat treating at 750° C. for 4 hours,illustrating the presence of pseudobrookite for which line broadeninganalysis suggests crystallite sizes of roughly between 15-20 nm.

The dielectric constant and loss tangent of selected glass-ceramics weremeasured from 400 to 3000 MHz on 12 mm long, 3.5 mm diameter rods atMicrowave Properties North (325 Wylie Road, Deep River, Ontario, CanadaKOJ1P0) using the cavity perturbation technique. Optical spectra weremeasured on a PerkinElmer Lambda 950 UV-Vis-NIR Spectrophotometer from2500 to 200 nm with 2 nm data interval using 0.8 mm thick samples. Insitu high temperature measurements were made on the same instrumentusing a joule heated hot stage with 0.5 mm thick 13 mm diameter samplesunder a nitrogen atmosphere to prevent oxidation of the stainless steelsample holder and maintain good thermal contact with the small sample.

FIG. 8 shows the average dielectric constant and loss tangent as afunction of R₂O—Al₂O₃ for glass-ceramics made from Example Compositions2-6, after ceramming at 750-4, over the frequency range of 400 to 3000MHz. FIG. 8 also shows the dielectric constant and loss tangent as afunction of R₂O—Al₂O₃ for glass-ceramics made from Example Composition7, after ceramming at 750-4, over the frequency range of 400 to 3000 MHz(shown as individual points in FIG. 8). These data represent acomposition set examining alkali to alumina contents at constant Fe₂O₃level plus Example Composition 7, with 2 mole % TiO₂ at R₂O—Al₂O₃=0.Since the dielectric constant K for each glass-ceramic varied by lessthan 4% over the frequency range measured, an average was used torepresent the featureless spectral data for simplicity. The loss tangentwas a linearly increasing function of frequency and increased by0.005+/−0.002 from 400 to 3000 MHz. The dielectric constant shows adiscontinuity versus excess alkali at the charge balanced compositionwhere R₂O═Al₂O₃, while the loss tangent was a sigmoidally decreasingfunction of excess alkali (R₂O—Al₂O₃). When 2 mole % SiO₂ from thecharge balanced composition of Example Composition 4 was replaced with 2mole % TiO₂ to make Example Composition 7, the cerammed phase shiftedfrom magnetite to pseudobrookite and the dielectric constant jumped to7.8 while the loss tangent increased to 0.027.

The black, magnetite-containing glass-ceramics provide the opacity andother desirable, non-magentic properties for electronic deviceapplications. In other applications, such as appliances, theglass-ceramics exhibit magnetic properties that are desirable. Theamount of TiO₂ in Example Composition 7 started to shift the crystallitephase away from magnetite as pseudobrookite and ε-Fe₂O₃ alsoprecipitated; however, the material spontaneously formed crystals in theannealed precursor glass and its loss tangent was the highest of all theglasses studied thus far. Consequently Example Compositions 14-17 and43-44 were formulated to explore the newly found pseudobrookite andε-Fe₂O₃ composition space and lower the total Fe₂O₃ content to decreasethe loss tangent.

The dielectric constant and loss tangent for glass-ceramics with a lowerFe₂O₃ content (e.g., glass-ceramics formed from Example Compositions 15,43 and 44, which are plotted in FIG. 9), show the large decrease indielectric constant and loss tangent with decreasing Fe₂O₃ content. Itshould be noted that Example Composition 43 also has a lower TiO₂content and a greater SiO₂ content than Example Compositions 15 and 44,which could also contribute to the more rapidly decreasing loss tangentand dielectric constant between 0.6 and 0.5 mole % Fe₂O₃.

FIG. 10 shows the transmission spectra of crystallizable glasses madefrom Example Composition 15 as a function of heat treatment. The samplesof crystallizable glass were placed on lined paper and had dimensions of25 mm×25 mm×0.8 mm. The samples were amber, yet transparent, afterannealing. After the samples were nucleated at 630° C. and cerammed at700° C. and 750° C., respectively, for 4 hours, they were pitch blackand opaque, even at a thickness of about 0.8 mm. The transmissionincreases at wavelengths longer than 1500 nm, with samples heat-treatedat lower temperature exhibiting higher IR transmission.

The kinetics of crystallization were investigated by measuring thetransmission of sheets of selected glasses during the ceramming process.An un-annealed sheet of glass was prepared from Example Composition 60and had a thickness of about 0.5 mm. The glass sheet was heated in a hotcell in a spectrophotometer. FIG. 11 shows the temperature of the sampleand the transmission as a function of time during heat up, nucleation,and crystal growth. The transmission at 400 nm diminished rapidly as thesample was heated to the 630° C. nucleation temperature. Thetransmission across the visible portion of the spectrum then followedsuit and slowly declined during the nucleation hold. Then thetemperature was raised to 700° C. near 200 min where the remainingtransmission plummeted to 0 over the next 60 minutes. The nucleationstep is significant and omitting the nucleation step and thus hold at630° C. results in samples with greater than 75% of the transmission ofannealed samples even with 4 hour holds at 700 or 750° C. The extinctionspectra of glass-ceramics made from Example Composition 53 after variousheat-treatments are plotted in FIG. 12. The UV edge shifts to longerwavelengths and the absorption band at 1100 nm increases up until aceram temperature of 750° C. At higher ceram temperatures, the 1100 nmabsorption band begins to diminish and the UV edge shifts back toshorter wavelength. This trend continues to 850° C. where the glassbegins to noticeably soften. The absorption at 650, 700, 1100, 1500,2000, and 2500 nm are plotted as a function of ceram temperature in theinsert in FIG. 12 to illustrate this behavior, clearly showing the peakin opacity at 750° C. An XRD confirmed that the phase remains ε-Fe₂O₃ at800° C. Decreasing opacity with increasing ceram temperatures above 750°C. was also observed visually with intense backlighting of the sampleand confirmed spectroscopically in glass-ceramics made from ExampleCompositions 15 and 43-44, 53, 57, 60, 63 and 71. The color of thesesamples was blackest for ceram temperatures between 700 to 750° C. andthen began to turn noticeably grey with increasing ceram temperatures ator above 775° C. Ceram temperatures below 700° C. resulted in ambersamples with visibly noticeable transmission.

The electron energy loss spectra (EELS) of the Fe and Ti in thenanocrystals of selected glass-ceramics made from the ExampleCompositions of Table 1 were measured to see if the opacity maximum wasthe result of an oxidation state change. At least 5 nanocrystals fromeach heat treatment were measured, curve fit to standard Fe²⁺ and Fe³⁺spectra and then plotted as a function of ceram temperature in FIG. 13.Glass-ceramics made from Example Compositions 53, 60, and 71 weremeasured and all showed a minimum in the Fe³⁺/Total Fe ratio at a heattreatment temperature of 775° C., indicating that Fe²⁺ in thenanocrystals is maximized with this heat treatment. Larger nanocrystalsin the sample were chosen from the thinnest section of the TEM sample toavoid signal from the glass and obliteration of smaller nanocrystalsfrom beam damage. Thus only a small fraction of nanocrystals weresuitable for analysis and each had significantly different compositions,so the ensemble average of analyzed crystals for each ceram temperatureis plotted in the FIG. 13 inset. The nanocrystallites in the 675 and700° C. heat treated samples were too small for analysis.

To obtain the EELS data, electron thin samples (<100 nm) of selectedglass-ceramics were prepared with a FEI Quanta focused ion beam (FIB)system using the very gentle sample preparation technique as describedbelow. The main pit was milled at 30 KeV 5 nA (20 um×10 um×2 um). Thefirst facing was done using 30 KeV at 1 nA to a thickness of 1 um. Toreduce damage to the sample during the preparation the final polishingwas done at 5 KeV at 150 nA to less than 100 nm. To remove the leftoverGa during the FIB-ing process the final cleaning was done at 2 KeV and0.083 nA. It has been hypothesized before that for every KeV increase inthe FIB voltage there is ˜1 nm thick damaged layer. Thus using the final2 KeV for cleaning, the damage layer is only ˜2 nm. To reduce damageduring imaging, the TEM was done at 80 KeV at a low extraction. Thisreduced the electron dose on the sample during imaging. The compositionof the particles was calculated. EELS spectra for Fe and Ti werecollected using a Gatan Quantum® GIF with high dispersion of 0.05eV/channel. As the zero loss peak (ZLP) had 0.8 eV resolution, it waspossible to capture all the salient features of the Fe and Ti L₂₃ edges.

FIG. 14A shows the TEM micrograph of a glass-ceramic made from ExampleComposition 60, after being cerammed at 750° C., for 4 hours. The imageof FIG. 14A shows the ˜20 nm crystallites, while the elemental maps ofFIG. 14B show that the crystallites are enriched in Fe, Ti, and Mg anddepleted in Si, Al, and Na. The compositions of at least 5 crystallitesfrom the glass-ceramics made from Example Compositions 53 and 71 weremeasured and averaged for each heat treatment by EELS and superimposedon the 1000° C. MgO—TiO₂—Fe₂O₃ phase diagram shown in FIG. 15. TheFe₂O₃, MgO, and TiO₂ contents of the Example Compositions 53 and 71,excluding other components, were also plotted for comparison. Thecrystallites in Example Composition 53 were almost spherical at alltemperatures similar to those in FIGS. 14A and 14B, while ExampleComposition 71 had additional elongated crystallites, so thecompositions of both morphologies were measured and plotted separatelyin FIG. 15. The crystallites formed at 675° C. and 700° C. were toosmall to analyze by TEM, but the 725° C. samples had ε-Fe₂O₃crystallites on the α′-Fe₂O₃ (hematite) α-MgTiO₃ (geikielite) tie linefor both glasses. As the ceram temperature was increased to 750° C., thecomposition of the crystallites shifted along the tie line towardsMgTiO₃. When cerammed at 775° C., the composition of the crystallites inthe glass-ceramic made from Example Composition 53 continued to enrichin MgTiO₃ at the expense of Fe₂O₃, while the crystallites of bothmorphologies in the glass-ceramic made from Example Composition 71 beganto shift to the TiO₂ rich side of the tie line at 775° C. At the 800° C.ceram temperature the elongated crystallites in Example CompositionGlass 71 were on the pseudobrookite tie line, the spherical crystals onthe α′-Fe₂O₃ (hematite) α-MgTiO₃ (geikielite) tie line, and the samplesexpressed both pseudobrookite and ε-Fe₂O₃ in XRD. X-ray diffraction datasuggests these correspond to the elongated and spherical crystallitesrespectively. The crystallites in both compositions became richer inFe₂O₃ as the ceram temperature was increased from 775 to 800° C. Thecompositions of the elongated crystallites in the glass-ceramics madefrom Example Compositions 53 and 71, after being cerammed at 850° C.were both on the pseudobrookite tie line with those of ExampleComposition 53 (i.e., close to pure Fe₂TiO₅).

Glass-ceramics samples were formed from Example Compositions 53 and 71.The crystallizable glasses were formed and nucleated at 630° C. for 2hours and then cerammed for 4 hours each at the temperatures shown belowin Table VI. Table VI also shows the elemental compositions of thecrystallites present in the resulting glass-ceramics formed from ExampleCompositions 53 and 71.

TABLE VI Elemental composition of crystallites. Morphology CerammingSpherical Crystals Elongated Crystals Temperature (mol %) (mol %) (° C.)Fe₂O₃ MgO TiO₂ Fe₂O₃ MgO TiO₂ Example Composition 53 725 39.7 29.8 30.544.1 23.4 32.5 750 23.4 39.3 37.3 21.1 43.1 35.9 775 22.8 36.7 40.5 18.940.1 41.0 800 55.5 16.1 28.4 61.0 14.1 24.9 Example Composition 71 72524.7 31.6 43.7 24.3 32.7 42.9 750 17.3 31.3 51.4 11.1 42.5 46.4 775 18.828.6 52.6 10.6 37.0 52.4 800 27.8 29.6 42.5 21.2 19.1 59.6

Glass-ceramic samples were formed from Example Compositions 57, 70, 71,114 and 53. The Example Compositions were nucleated for 2 hours at 630°C. and cerammed at the temperatures shown in FIG. 16. The resultingglass-ceramics had a thickness of about 0.8 mm. It was observed thatglass-ceramics formed from these Example Compositions having about 1-2wt % Fe₂O₃, about 1-2 wt % TiO₂, about 0-0.5 wt % MnO₂ and 0-0.5 wt %SnO₂ all exhibited a dark black color. Increasing the cerammingtemperature, however, changed the opaque glass-ceramics from exhibitinga black color to a gray color, which can increase the transmission. Itwas observed that at peak ceramming temperatures of about 775° C. orgreater, the color of the glass-ceramics turned from black to gray. FIG.16 shows a drastic increase in transmission through the samples as theceramming temperature was increased above 725° C. The glass-ceramicsexhibiting a greater L* value exhibited higher transmission and, in somecases, exhibited an amber color.

To understand the causes of the changes in optical properties (e.g., L),Example Compositions 52, 60 and 71 were evaluated in greater detail withrespect to the change in Fe/Ti ratio. As shown in Table VII, ExampleComposition 60 had the highest Fe content (an greatest Fe/Ti ratio) andExample Composition 71 had the lowest Fe content (and lowest Fe/Tiratio).

TABLE VII Fe/Ti and Fe/Mg ratio of Example Compositions 53, 60 and 71.Example Composition 71 53 60 Fe/Ti 1.02 1.16 1.43 Fe/Mg 1.65 1.28 1.6

Glass-ceramics were formed from Example Compositions 53, 60 and 71 bynucleating the crystallizable glasses at 630° C. and ceramming at 800°C. for 4 hours or 775° C. for 4 hours. FIGS. 17-19 show the XRD tracesof the glass-ceramics formed from Examples 53, 60 and 71. As shown inFIG. 17, the glass-ceramics formed from Example Composition 71 showpredominantly pseudobrookite and little ε-Fe₂O₃. As shown in FIGS.18-19, the glass-ceramics formed from Example Composition 53 and 60(which were cerammed at a lower temperature of about 775° C.) exhibitedpredominantly ε-Fe₂O₃ crystals. The data from FIGS. 17-19 indicates thatabove a certain Fe/Ti ratio, the final crystallites in theglass-ceramics include ε-Fe₂O₃. Where the content of Ti is higher,crystallites include pseudobrookite. This is represented in the phasediagram (Fe₂O₃—FeO—TiO₂) shown in FIG. 20. Pseudobrookite is a solidsolution of Fe^(III) ₂TiO₅ and Fe^(II)Ti₂O₅ and is black in color, butnot magnetic.

FIG. 21 shows high angle annular dark field (“HAADF”) or Z-contrastimages of a glass-ceramic formed from Example Composition 53, afternucleating at 630° C. for 2 hours and ceramming at 800° C. for 4 hours.The corresponding Energy Dispersive X-Ray Spectroscopy (EDS) maps of Fe,Ti and Mg elements are also shown in FIG. 21. The brighter or lightercolored areas indicate crystalline areas. The length scale at the bottomof each EDS map indicates 200 nm. The EDS maps show the presence of Mgin all the particles of the glass-ceramic. In the Example Compositionsshown in FIG. 21, Mg was detected in the crystals for all thecompositions, cerammed at different temperatures.

Various glass-ceramics were made from Example Compositions 53 and 71 andcerammed at different temperatures. FIGS. 22A and 22B shows thegraphical representation of the quantitative data with cerammingtemperature. The data indicates that for glass-ceramics made fromExample Compositions 53 (and which include both spherical and elongatedmorphological particles), the Fe content in the crystallites decreasesas the ceramming temperature increases from 725° C. to 750° C. and theamount of Mg and Ti increases. When the ceramming temperature is 750°C., the mol % of both Fe and Mg in the crystallites varied between 25mol % to 35 mol %. When the ceramming temperature exceeded 750° C., Mgand Ti in starts to leave the crystallites and the crystallites becomerich in Fe. This conclusion corresponds well with the transmission dataof FIG. 16, which shows a minima at the ceramming temperature of 750° C.The data for glass-ceramics formed from Example Composition 71, whichincludes a higher TiO₂ content relative to Example Compositions 53 and60, differs. The composition of the elongated crystallites in theglass-ceramics formed from Example Composition 71 shows a steadyincrease in Ti as ceramming temperature increases, but the amount of Feand Mg in the crystallites follows the same trend as the glass-ceramicsfrom Example Composition 53. On the other hand, the sphericalcrystallites follow the same trend as the glass-ceramics formed fromExample Composition 53, but the composition of the individual elements(Fe, Ti and Mg mol/%) is different. In the glass-ceramics formed fromExample Composition 71, both the spherical and elongated crystallitesinclude Fe and Mg in the range from about 25 mol % to 35 mol % at 725°C. The spherical particles (which include the majority of thecrystallites) maintains this composition even when the cerammingtemperature is increased to 775° C.; however, the elongated particles(which include the minority of the crystallites) have an increasedamount of Ti (in mol %). Transmission data from FIG. 16 supports thisbecause transmission remains almost constant up a ceramming temperatureof 750° C., after which transmission starts increasing. Thus, withoutbeing bound by theory, it appears that to achieve the lowesttransmission, the Fe and Mg content in the majority of the crystallitesshould be maintained in the range from about 25 mol % to about 35 mol %.These values of the particles are plotted on the MgO—Fe₂O₃—TiO₂ phasediagram (in wt %) as shown in FIG. 15. The crystals from theglass-ceramics made from Example Composition 53 lay right on top of theFe₂O₃—MgTiO₃ (ε-Fe₂O₃) tie line. The crystallites in the glass-ceramicsmade from Example Composition 71 are enriched in TiO₂ relative to thetie line. Glass-ceramics made from either composition and cerammed atthe highest ceramming temperature (i.e., 800° C.) exhibited the highestFe content crystallites and the glass-ceramics that exhibited the nexthighest Fe content crystallites were cerammed at the coolest cerammingtemperature (i.e., 725° C.). The glass-ceramics that were cerammed atintermediate ceramming temperatures (e.g., 725° C. and 750° C.)exhibited the darkest color and the lowest amount of Fe. Thus the darkglass-ceramic formed from Example Composition 53 (nucleated at 630° C.for 2 hours and cerammed at 750° C. for 4 hours) have crystallites withabout the same composition as the crystallites of fading glass-ceramicsformed from Example Composition 71 (nucleated at 630° C. for 2 hours andcerammed at 800° C. for 4 hours).

FIG. 23 shows the Fe L₂₃ ELNES for crystallites from glass-ceramics madefrom Example Composition 53, with increasing ceramming temperatures. TheFe³⁺ main edge is at 709.1 (±0.1) eV with a small shoulder at 707.7 eV.On the other hand the Fe²⁺ edge is at a707.3 (±0.1)eV. The ELNES showsthat the crystallites after ceramming at 725° C. are predominantly Fe³⁺,but the amount of Fe²⁺ in the particles increases with increasingceramming temperature up to 775° C. The amount of Fe²⁺ is then reducedand the crystallites go back to being predominantly Fe³⁺, after thistemperature. This change in Fe³⁺ and Fe²⁺ with ceramming temperature issupported by the compositional analysis in which the amount of Mg²⁺ ionsin the crystallites increases at ceramming temperatures greater than725° C., to charge balance some of the Fe³⁺ changes to Fe²⁺. Atceramming temperatures above 775, the amount of Mg²⁺ ions decreases andthe Fe returns to its original oxidation state. This indicates that thepresence of Fe³⁺ and Fe²⁺ within a crystal provides the desirable blackcolor in glass-ceramics. The oxidation state of Fe is consideredsignificant because, the presence of Fe²⁺ ions are next to Ti ionsprovides a black color, whereas, the presence of Fe³⁺ ions provides ablue or green color. The interaction of Fe²⁺ and Fe³⁺ ions may alsoprovide some additional color, thus enhancing absorption.

The change in color in the glass-ceramics described herein at higherceramming temperature could be due to mixture of two differentphenomenon: effects due to composition and effects due to scattering.Scattering in these glass-ceramics is due to either an increase inparticle size or an increase in the amount (area fraction) of thecrystallites in the glass matrix. Without being bound by theory, it isbelieved that increased scattering is related to the gray colorationobserved after ceramming at higher temperatures. FIG. 24 showsrepresentative HAADF STEM images of glass-ceramics made from ExampleComposition 53, after being cerammed at 725° C., 750° C., 775° C. and800° C. Qualitatively, the images of FIG. 24 show a progressive increasein the amount of crystallites as the ceramming temperature increases.

HAADF STEM images of glass-ceramics made from Example Composition 73were also taken at different ceramming temperatures. Image analysis wasperformed on 4-5 of the images at each temperature to calculate the areafraction and percentage of different particle morphology within theglass matrix of the glass-ceramic. The averages of these values areshown in FIGS. 25A, 25B and 25C. Image analysis shows that inglass-ceramics made from Example Compositions 53 and 71, the areafraction of particles is below about 10% at ceramming temperatures up toabout 775° C. As such, it is believed that to minimize the effect ofscattering and to achieve a black color, the area fraction of thecrystallites in a glass-ceramic may be below about 10%.

Image analysis also indicated that in glass-ceramics made from ExampleComposition 71, there is a significant increase in spherical particlesand a reduction in elongated particles, which are also Ti-rich. Thisdifference suggests that the color exhibited by these glass-ceramics isdue to the presence of spherical particles and not the Ti-rich elongatedparticles.

Other analysis included the CIELAB color space coordinates determinationand phase identification by x-ray diffraction.

Among the further processing was an ion exchange treatment of theglass-ceramics. Each glass-ceramic sample was cut into shapes suitablefor ion exchange evaluation. The samples are then cleaned to eliminateany residual organic contamination. Each cleaned sample is suspended ina bath of molten KNO₃ and held at between 370° C. and 450° C. After anappropriate number of hours in the bath (e.g., up to about 8 hr ormore), the sample is removed, allowed to cool, and washed in deionizedwater to remove any residual salt. Glass-ceramics according to ExampleComposition 1-7, 14-17, 43-44, 53, 57, 60, 63 and 71 were immersed in amolten bath of potassium nitrate (with 0.5 wt % silicic acid to preventetching) having a temperature of about 420° C. or 430° C. between 6.5and 8 hours in 304 stainless steel containers and baskets. Theglass-ceramic samples were then cooled to room temperature, and thenwashed in deionized water to remove the adhered salt. Following suchtreatment, the compressive stress and depth of layer were measured usingpolarized light on an Orihara surface stress meter model FSM-6000 forglasses and an instrument operating at 1550 nm in the NIR to measure theglass-ceramics, which were opaque in the visible spectrum. Stressoptical coefficient and refractive index were measured by diametricalcompression and critical angle methods respectively to convert FSMbirefringence into stress and depth of layer. FIG. 6, shows DOL as afunction of CS for selected glass-ceramics. FIG. 6 also shows thepossible CS/DOL combinations that were achievable in the glass-ceramicsdescribed herein, using different ion exchange patterns. For example, itis possible to provide glass-ceramics having a CS 900-1100 MPa and DOLof between 25-55 microns.

The mechanical performance of the black glass-ceramics obtained fromExample Compositions 53 and 60 were measured by three methods: flexuralresponse by ring on ring (ROR) and abraded ring on ring (aROR), and 4point bend. The ring on ring test evaluates the biaxial flexure strengthof the substrate faces, while the 4 point bend test evaluates thestrength and finish quality of the edges. Abraded ring-on-ring was usedto quantify retained mechanical performance, after having imposed agiven flaw population.

Ring on ring strength (biaxial flexure) was measured on 50 mm squaresamples having a thickness of about 0.8 mm using a 25.4 mm support ringand 12.7 mm load ring and crosshead speed of 1.2 mm/min according toASTM C1499. To rank the relative strength of the materials after use,samples were abraded with SiC grit according to ASTM C158.

The strength attributes of a commercially available aluminosilicateglass substrate (shown as “Substrate X” in Table VIII and FIGS. 26-28)and the glass-ceramics formed from Example Compositions Glasses 53 and60, after being heat treated at 700-4 were compared. Both the SubstrateX and the glass-ceramic samples were ion-exchanged to the same depth oflayer. The glass-ceramics were ion exchanged at a higher temperaturethan the Substrate X samples as shown in Table VIII, to better match thecompressive stress of the Substrate X samples.

TABLE VIII Heat treatment and ion exchange conditions and resultingstrength properties. Glass- Glass- ceramic ceramic formed formed fromfrom Ex. Ex. Substrate Comp. Comp. Sample X 53 60 Heat Nucleation (°C.-hr) None 630-2 630-2 Treatment Growth (° C.-hr) None 700-4 700-4 IXTemperature (° C.) 420 430 430 Time (hr) 6.5 8 8 CS (MPa) 848 998 1060DOL (μm) 43 41 41 Strength ROR (N) 2350 2852 2974 aROR (N) 961 1284 13214 pt Bend (MPa) 709 838 848

FIG. 26 shows the ring on ring load to failure distribution of 30samples of the glass-ceramics and Substrate X, both before and after ionexchange (all samples had a thickness of about 0.8 mm). Load to failureis reported because the strength of the ion exchanged samples was sohigh that bending displacement was large enough to make the membranestresses non-negligible. Therefore, conventional failure stresscalculations would overestimate the material stress at failure. Whilestrain gauges would enable calculation of the true stress, they increasethe stiffness of the sample and alter the very surface under test andcreate an additional source of error. Thus, rather than report aninflated strength value (stress at failure) Table VIII and FIG. 26 showsthe load to failure which is directly measured without any assumptionsor estimations for an unbiased ranking of relative strength for thebiaxial flexure tests. The Weibull modulus and characteristic life,which is the 63.2 percentile (1-1/e) of the data, are reported in FIGS.26-28 for comparison. Before ion exchange, comparative Substrate X had acharacteristic life load of 381 N, while the glass-ceramics made fromExample Compositions 53 and 60 exhibited similar characteristic lifeloads of 437 and 459 N, respectively. After ion exchange, the lifetimeload to failure for Substrate X increased to 2371 N, the glass-ceramicformed form Example Composition 53 increased to 2825 N and theglass-ceramic formed from Example Composition 60 increased to 2965 N.The 95% confidence intervals (dashed lines) of both glass-ceramics inFIG. 16 were overlapping indicating no significant difference betweenthem, but both were significantly higher than Substrate X. The slopes ofthe failure probability lines significantly steepened with ion exchange,increasing the Weibull modulus from between 2.9 and 4.6 for the non-ionexchanged glass-ceramic and Substrate X samples up to between 15 and 19for the ion exchanged glass-ceramic and Substrate X samples.

To determine the biaxial performance after in-use conditions, the partswere abraded with 1 ml of SiC particles at 34 kPa pressure and thentested using the same ring-on-ring test configuration as used in FIG.26. Abrasion in this way imposes flaws of roughly 20 μm in depth andserves as a surrogate for what the material being tested would encounterin the field. FIG. 27 shows that Substrate X samples, glass-ceramicsamples made from Example Composition 53, and glass-ceramic samples madefrom Example Composition 60 had 961 N, 1283 N, and 1321 N characteristiclife loads, respectively. Once again, the two glass-ceramics wereindistinguishable, and significantly better than the glass. All hadsimilar Weibull moduli between 6 and 9. The four point bend data shownin FIG. 28 shows that the non-ion exchanged samples all hadcharacteristic strengths between 120 and 140 MPa. After ion exchange,the Substrate X samples strength increased to 709 MPa, while thestrength of the glass-ceramic samples made from Glasses 53 and 60increased to 838 and 848 MPa, respectively, all with Weibull modulibetween 35 and 60. Both glass-ceramics were significantly stronger thanSubstrate X, but indistinguishable from each other.

While crystallizable glasses formed from Example Composition 1 exhibiteda liquidus viscosity of about 1.2 kPa*s, crystallizable glasses formedfrom Example Compositions 53 and 71 exhibited liquidus viscosities thatexceeded 100 kPa*s. All of the glasses measured had strain points near560° C., anneal points close to 615° C., and softening points near 895°C. The spontaneous magnetite precipitation in the crystallizable glassmade from Example Composition 1 indicates that 2.16 moles of Fe₂O₃exceeds the solubility limit for this composition. This is alsomanifested as a high liquidus temperature of 1235° C. with magnetite asthe liquidus phase. Example Composition 1 may be useful for aspontaneous black magnetic glass-ceramic, it would not be suitable formaking precision glass sheets, due to its low liquidus viscosity of 1.2kPa*s.

Example Compositions 2-6 showed the large impact of excess alkali(R₂O—Al₂O₃) on Fe₂O₃ solubility. Example Composition 2 with 2 moles ofexcess alkali is grossly under-saturated in Fe₂O₃ and remained amorphouseven after ceramming. Decreasing the excess alkali to 1 mole % resultsin a stable glass, that cerams to a black magnetite glass-ceramic, withjust over 40 kPa*s liquidus viscosity—more than adequate for any formingoperation. Once the alumina content exceeds the alkali, spontaneousmagnetite precipitation is now even observed at 1.8 mole % Fe₂O₃demonstrated by Example Compositions 5 and 6.

The excess alkali also affected the dielectric properties of theglass-ceramics. The lower solubility of magnetite on the alumina richside of FIG. 8 resulted in more magnetite precipitating andcorrespondingly, a higher loss tangent. This was verified with XRD thatshowed the glass-ceramics exhibited increased integrated magnetite peakintensity at negative R₂O—Al₂O₃ that decreased to 0 as the excess alkaliwas increased to 2. Magnetite nanocrystals are reported to have a highdielectric loss tangent around 1.2 at about 3 GHz and magnetic lossesaround 0.5 depending of the size and structure of the magnetiteparticles. Thus the magnetite loss in known materials is 50 timesgreater than glass-ceramics made from Example Compositions 2-6, whichcould contain at most 1.2 mole % Fe₃O₄ implying the minority magnetitephase in these glass-ceramics contributes 1.2 loss tangent*1.2%=0.014 tothe loss tangent or the majority of the 0.025 loss tangent ofglass-ceramics made from Example Composition 6. However, the Fe₂O₃ freeglass of FIGS. 26-28 has a dielectric constant of 7.17 and an averageloss tangent of 0.022, which is only 0.003 less than the glass-ceramicmade from Example Composition 6 (which includes magnetite). It has alsobeen demonstrated that the loss tangent of magnetite could be reduced bymore than an order of magnitude by keeping the fine magnetite dispersedand free of large particles. This explains why the magnetite-containingglass-ceramics have a lower than expected loss tangent that is only0.003 higher than the iron free glass.

Since magnetite raises the dielectric loss tangent and causes magneticinterference, TiO₂ was added to Example Compositions 7, 14-17, 43-44,53, 57, 60, 63 and 71, to avoid the formation of magnetite and othermagnetic phases. The presence of TiO₂ shifted the phase out of magnetiteand into ε-Fe₂O₃ at TiO₂/Fe₂O₃ ratios between 1 and 2, and intopseudobrookite (Fe₂TiO₅—MgTi₂O₅ ss) as the TiO₂/Fe₂O₃ ratio approachedor exceeded 2 in Table I. The formation of the ε-Fe₂O₃ phase issurprising since ε-Fe₂O₃ is very hard to make, requiring oxidation ofatomized iron in an electric discharge or the transformation ofnanoparticles of γ-Fe₂O₃ (maghemite) well dispersed in a silica gel,none of which even yield phase pure ε-Fe₂O₃. In one or more embodiments,the formation ε-Fe₂O₃ is enhanced by keep the particles well dispersed.If the particles are allowed to agglomerate, they convert to maghemiteat elevated temperatures. ε-Fe₂O₃ is a non-collinear ferrimagnet with aCurie temperature near 200° C. and has a very large coercivity of 20 kOeand saturation magnetization of 25 emu/g; however the ε-Fe₂O₃ glassceramics of the embodiments described herein did not stick to a magnetlike the magnetite glass-ceramics.

The lack of obvious magnetism may be explained by the understanding thatsmall ε-Fe₂O₃ particles synthesized at 700° C. were superparamagneticexhibiting zero remnant magnetization and zero coercivity. It is alsounderstood that ε-Fe₂O₃ particles must reach a threshold size before itsmagnetocrystalline anisotropies could cause high coercivities and thatlow magnetization is achieved with small ε-Fe₂O₃ particles as the TEMimages depict. Furthermore, FIGS. 14A, 14B and 15 demonstrated that thenanocrystallites in the glass-ceramics with the ε-Fe₂O₃ structure arenot pure Fe₂O₃, but a solid solution of MgO, TiO₂, and Fe₂O₃, whichcould disrupt the magnetic ordering of ε-Fe₂O₃ made up of Fe₂O₃ alone.The glass-ceramics described herein also have a large fraction of Fe²⁺,unlike the pure Fe₂O₃ based ε-Fe₂O₃ which is nominally all Fe³⁺.Finally, all of the glass-ceramic compositions that expressed ε-Fe₂O₃had 2.4 times less total Fe₂O₃ than those expressing magnetite, so thetotal number of unpaired spins is lower in the ε-Fe₂O₃ glass-ceramicsreducing the magnetization by more than half. Thus, the small size,compositional complexity, mixed valence state, and lower total Fecontent all can contribute to the fortuitously low magnetization of theε-Fe₂O₃ glass-ceramics.

It was also noticed that the compositions of the ε-Fe₂O₃ nanocrystalsplot right across the gap in the rhombohedral phase field (α′-Fe₂O₃(hematite) α-MgTiO₃ (geikielite) tie line) in FIG. 15. It has beenreported that the gap gets smaller with decreasing temperature, but thishas not been investigated below 1000° C. due to slow equilibrationkinetics. However it is understood that the gap in the α′-Fe₂O₃(hematite) α-MgTiO₃ (geikielite) tie line should disappear in thevicinity of 700° C., which is the temperature regime where theglass-ceramics described herein form ε-Fe₂O₃. The ε-Fe₂O₃ inglass-ceramics made from Example Compositions 53 and 60 both convert topseudobrookite when cerammed at 850° C. It should also be pointed outthat the pseudo ternary diagram in FIG. 15 is an oversimplification ofthe crystallite compositions in this glass-ceramic because both Fe²⁺ andFe³⁺ are simultaneously present (bulk precursor glasses have about 2/3Fe³⁺ and 1/3 Fe²⁺). The FeO—TiO₂—Fe₂O₃ ternary in FIG. 29 has the samephase relationships as the MgO—TiO₂—Fe₂O₃ diagram in FIG. 15, exceptthat MgO is replaced by FeO and the rhombohedral phase extends all theway from α′-Fe₂O₃ to α′-FeTiO₃, unlike the Fe₂O₃—MgTiO₃ solid solutionwhich exhibits a gap in the middle that decreases with temperature. TheMgFe₂O₄ spinel has the same structure and similar XRD pattern to Fe₃O₄(FeFe₂O₄) magnetite so it is very likely the magnetite phase detected byXRD is actually a solid solution of both spinels, MgFe₂O₄ and Fe₃O₄.FIG. 29 shows that the gap disappears when MgO is replaced with FeO, andthe ε-Fe₂O₃ crystallites have a mixture of both MgO and FeO. Finally,ε-Fe₂O₃ is orthorhombic with a different crystal structure than therhombohedral isomorphs of α′-Fe₂O₃, α′-FeTiO₃, and α-MgTiO₃. Whileε-Fe₂O₃ may be metastable, metastable phases can often be formed fromthe crystallization of glass because metastable phases often requireless structural rearrangement from the glass than the stable phase wouldrequire. Thus the combination of well dispersed crystals, compositionalcomplexity, low ceram temperature, different structure, andprecipitation from a glass all can contribute to the stability of theε-Fe₂O₃ phase and its extensive solid solution.

While TiO₂ additions enabled the formation of non-magnetic black glassceramics, they also increased the dielectric constant and loss tangentof the glass-ceramic. By lowering the amount of ε-Fe₂O₃ and orpseudobrookite to the minimum amount needed to achieve the desiredcolor, the dielectric constant and loss tangent can both be lowered backto below 7.1 and 0.023 respectively as demonstrated by the glasses madefrom Example Compositions 15, 43 and 44 plotted in FIG. 9, which iscomparable to the Example Compositions of FIGS. 26-28 with 7.17dielectric constant, and 0.022 average loss tangent. As a benefit, thelower the amount of the low solubility phase, the lower the liquidustemperature, and correspondingly the liquidus viscosity will be greater.

By taking the low loss of Example Composition 43 and then fine tuningthe composition while keeping the minimal amounts of Fe₂O₃ and TiO₂necessary to achieve opacity and color, the high liquidus viscosityglass-ceramic made from Example Composition 53 was achieved with 135.8kPa*s liquidus viscosity. An even darker glass-ceramic was achieved byincreasing the Fe₂O₃ in the composition by only 0.15% resulting inExample Composition 60, which forms a clear glass, but was completelyopaque after ceramming, even with a thickness of about 0.8 mm, yet stillhad well over 60 kPa*s liquidus viscosity. A benefit of having a clearor transparent glass is that it permits for automated real timeautomated inspection of defects and assessment of quality before thematerial is cerammed. A transparent precursor glass is thus recognizedas a benefit in manufacturing, since a spontaneous black material wouldmask the quantity and identity of melting defects such as cord, seeds,knots, and stones that operators need to adjust melting conditions.These defects must be detected swiftly and the melting process tuned toeliminate them, since they can degrade the strength and performance ofthe material.

To fine tune the color and optimize the heat treatment time ofglass-ceramics made from Example Composition 60, the transmission wasstudied using in-situ transmission measurements during a ceram cycle.The transmission decrease during the 630° C. nucleation hold in FIG. 11indicates substantial changes occurring in the glass, even thoughneither TEM nor XRD could detect any signs of crystallization forsamples heat treated at 630° C. Without being bound by theory, it isbelieved that this must be when the nuclei form and that they are toosmall for either technique (i.e., TEM and/or XRD) to detect withoutdamaging the glass. Difficulty in observing the nucleating phase is notunusual even in ‘traditional’ high crystallinity glass-ceramics but inthe case reported here, these materials have less than 2 mole % of thecomposition available to partition into the crystal. If only a smallfraction of that 2 mol % is converting to nuclei, it can be extremelyhard to detect. Since the precursor glass is designed to respondthermally and ceram, it is very beam sensitive in the TEM andcrystallites below 5 nm cannot be imaged without damaging the glass, norcan meaningful EELS spectra be acquired on features smaller than 15 nm.The precipitous drop in transmission at 700° C. corresponds to thegrowth temperature of the crystallites.

The maximum in blackness and opacity at a ceramming temperature of about750° C. followed by diminished opacity and greying at highertemperatures was initially believed that the nanocrystallites weredissolving back into the glass at higher temperatures, but the TEMimages showed even larger crystallites with higher ceram temperatures.The areal density of the nanocrystallites was calculated from the TEMimages and plotted in FIG. 30 showing an increase in crystallinity withincreased ceram temperature, which rules out decreased crystallinity, asthe cause of diminished opacity and greying.

The shape of the absorption curves in FIG. 12 coupled with the Fe EELSspectra in FIG. 13 provides insight in understanding the transmissionincrease with ceram temperatures above 750° C. While the shape of theabsorption tail between 400 and 700 nm may resemble scattering, itfollows neither a λ⁻⁴ dependence indicative of Rayleigh scattering, nora λ⁻² dependence indicative of larger particle Mie scattering. It isactually well fit by a λ⁻³ dependence and is most likely the tail of thestrong absorption in the visible that makes the material black. Ifscattering were dominating extinction in the visible, the material wouldlook hazy or white. Accordingly, intense absorption is necessary to makea material black.

The Fe²⁺—Ti⁴⁺ charge transfer band has a very large absorption crosssection and results in intense absorption in the visible portion of thespectrum. Even a few tens of ppm of Fe²⁺ and Ti⁴⁺ result in a yellowtint that is detectable by eye. For charge transfer mechanisms to beactive, the Fe²⁺ and Ti⁴⁺ must be in close proximity such as nextnearest neighbors bound to a common O²⁻ ion. Even though both Fe²⁺ andTi⁴⁺ are present in the precursor glass, they are at low concentrations,and thus fairly well dispersed resulting only in a dark amber coloredglass due to the few Fe²⁺ and Ti⁴⁺ ions in close proximity. However whenthey are partitioned into the crystallites, they become next nearestneighbors creating an intense absorption band covering most of thevisible spectrum. Close inspection of FIG. 12 shows the Fe²⁺ band at1100 nm reaching a maximum at the 750° C. ceram temperature and thendiminishing at higher ceram temperatures in agreement with the 750° C.opacity maximum. The intensity of the charge transfer band must be 0 inthe absence of Fe²⁺ and then increases as the Fe²⁺ increases withoptimized ceram temperatures.

The EELS spectra of the nanocrystallites provide their composition aswell as the Fe²⁺ fraction. The highest fraction of Fe²⁺ occurs at theminimum in Fe³⁺/Total Fe ratio in FIG. 13 at the 775° C. ceramtemperature, which is 25° C. hotter than the observed opacity maximumand Fe²⁺ peak in the optical data. FIG. 31 shows the total Fe²⁺concentration from EELS (Fe²⁺ fraction*Total Fe₂O₃) as well as the MgOcontent of the crystallites. While the Fe²⁺ peaks at a ceram temperatureof 775° C., the MgO peaks at a ceram temperature of 750° C. in agreementwith the observed opacity maximum. Fe²⁺—Fe³⁺ and Fe²⁺—Ti⁴⁺ coordinationclusters may coexist in the same structure and give rise to bothhomonuclear Fe²⁺—Fe³⁺ as well as heteronuclear Fe²⁺—Ti⁴⁺ charge transferbands. The optical absorption data indicates the largest Fe²⁺concentration occurs at the 750° C. ceram temperature, so there shouldbe an accompanying maximum in both Fe²⁺—Fe³⁺ and Fe²⁺—Ti⁴⁺ coordinationclusters and charge transfer absorption, since both clusters requireFe²⁺. In addition, it is understood that the local charge misbalancethat occurs with the isomorphous substitution of ions facilitateshomonuclear charge transfer bands, such as the replacement of Fe²⁺ andMg²⁺ by Al³⁺ and Fe³⁺ in ferromagnesian silicates. In the case ofε-Fe₂O₃, all of the cations are nominally Fe³⁺, so for the structure toaccommodate Mg²⁺ and Fe²⁺, Ti⁴⁺ ions or oxygen vacancies must compensatethe charge deficit. Either will result in local charge imbalance to liftthe degeneracy of the Fe sites giving rise to homonuclear Fe²⁺→Fe³⁺.Thus the higher levels of Mg²⁺ and Fe²⁺ in the ε-Fe₂O₃ crystallites arecorrelated with the opacity of the glass-ceramics and likely explain theabsorption maximum at the 750° C. ceram temperature via the greatertotal absorption intensity of the Fe²⁺—Fe³⁺ and Fe²⁺—Ti⁴⁺ chargetransfer bands. At the higher ceram temperatures where the crystallitesare larger and the Fe²⁺—Ti⁴⁺ charge transfer band diminished, scatteringbecomes significant. Pure scattering makes a white material, but whenmixed with black, results in the greys observed in the samples cerammedat 800 and 850° C.

The ring-on-ring data provided herein demonstrate that the glass-ceramicmechanical performance and surface finish were no different from that ofknown glass substrates before ion exchange. After ion exchange, thefailure load for the glass and glass-ceramics was increased by a factorof about 6 because the compressive stress induced by the ion exchangeprocess put approximately 1 GPa of compression onto any existing flawsnear the surface of the glass or glass-ceramic. This chemically inducedcompression then needs to be overcome before the flaws can experiencetension and subsequent failure. Abraded ring-on-ring data provided anindication of how the material will perform in the field after use, oncedamage and flaws have been introduced. The black glass-ceramics showedslightly better performance in both the abraded and non-abraded tests.To understand why, the ring-on-ring and 4 point bend results wereplotted as a function of ion exchanged compressive stress in FIG. 32which shows the correlation between compressive stress and load tofailure. It should be noted that the 4 point bend measured modulus ofrupture, and not edge strength. For samples with the same nominalexchange depths, the higher compressive stress puts a greatercompressive force on existing flaws as well as a greater compressivestress below the surface at the depth the damage was driven by abrasion,which is typically on the order of 10 microns deep and well within the41 micron compressive layer.

It was observed that the compressive stress was higher for theglass-ceramics than the glass Substrate X samples, even though the glassceramics were ion exchanged for longer time at a hotter temperature,both of which typically reduce the compressive stress for an ionexchanged glass. One reason for this may be that the glass Substrate Xsamples were quenched into air after fusion draw, while theglass-ceramics were also initially quenched, but they were subsequentlycerammed and cooled much slower in an oven at furnace rate resulting ina denser residual glass in the glass-ceramic. It has been demonstratedthat annealed glasses have higher compressive stress and lowerdiffusivities than quenched glasses. Without being bound by theory, thismay be why the slowly cooled glass-ceramics have higher compressivestress and strength than their glass counterpart. Without being bound bytheory, this may also be the reason why the glass-ceramics needed to beion exchanged 10° C. hotter and 1.5 hours longer to achieve the same DOLas the Substrate X samples.

The foregoing embodiments describe crystallizable glasses that providelow crystallinity glass-ceramics with high liquidus viscosity.Magnetite, pseudobrookite, and ε-Fe₂O₃ glass-ceramics were made by heattreating silicate glasses doped with Fe₂O₃, MgO, and or TiO₂. Extensivesolid solution of ε-Fe₂O₃ with MgTiO₃ was discovered for ceramtemperatures between 675 and 800° C. EELS and optical absorption datashowed that the Fe²⁺ content of the crystallites reached a maximum near750° C. resulting in maximum blackness and opacity because of optimizedFe²⁺—Ti⁴⁺ charge transfer. By keeping the amount of crystalline materialminimal, the dielectric losses and liquidus temperatures were minimizedproviding a first fusion formable oxide glass-ceramic. Utilizingcrystallizable glass compositions with fast ion exchange properties andhigh compressive stress, resulted in glass-ceramics with strengths of840 to 850 MPa after ion exchange.

Example Compositions 116-170: The Example Compositions listed in TableIX were used to form crystallizable glasses by introducing appropriatelybatched raw materials to a platinum crucible. The crucible was thenplaced in a furnace having a temperature up to about 1700° C. Thematerials were then refined and the molten glasses were then eitherpoured onto a steel plate to make patties of glass, or they were formedinto sheet by rolling or down draw.

In particular, crystallizable glasses formed from Example Compositions116-170 were melted by mixing 2500 g of batched raw materials in a 1.81platinum crucible, which was then placed in a SiC globar furnace havinga temperature of about 1600° C. for 5 hours. The melted materials werethen poured a thin stream into a bucket of flowing cold water to makecullet. The cullet was then remelted at 1650° C. for 5 hours to obtain ahomogeneous melt and then poured onto a steel table and subsequentlyannealed for 2 hours at about 620° C.

TABLE IX Ex. SiO₂ Al₂O₃ B₂O₃ Li₂O Na₂O K₂O MgO CaO SnO₂ 116 64.27713.240 5.369 0    13.794 0.002 2.040 0.036 0.003 117 64.306 13.267 5.2410    13.881 0.002 1.546 0.031 0.003 118 64.404 13.327 5.188 0    13.7940.002 1.274 0.031 0.003 119 64.357 13.297 5.173 0    13.835 0.002 1.8980.035 0.003 120 64.201 13.274 5.298 0    13.902 0.001 1.805 0.033 0.003121 64.248 13.267 5.282 0    13.902 0.002 1.693 0.032 0.003 122 66.71011.880 6.750 4.420 6.790 0.480 1.570 0    0    123 63.908 13.579 5.3550    13.784 0.018 1.554 0.032 0.038 124 63.904 13.557 5.364 0    13.7840.019 1.553 0.032 0.042 125 63.829 13.526 5.371 0    13.849 0.019 1.5510.032 0.042 126 63.753 13.496 5.378 0    13.915 0.019 1.550 0.031 0.042127 63.866 13.506 5.384 0    13.826 0.020 1.534 0.031 0.039 128 63.83113.525 5.386 0    13.805 0.019 1.531 0.047 0.042 129 63.829 13.530 5.4100    13.819 0.018 1.502 0.035 0.038 130 63.885 13.430 5.404 0    13.8490.017 1.524 0.032 0.040 131 63.849 13.467 5.403 0    13.853 0.017 1.5220.031 0.038 132 63.850 13.443 5.406 0    13.858 0.019 1.525 0.030 0.038133 63.811 13.396 5.406 0    13.960 0.018 1.523 0.030 0.036 134 63.96713.447 5.350 0    13.794 0.018 1.515 0.031 0.043 135 63.899 13.458 5.3730    13.838 0.019 1.518 0.030 0.041 136 63.833 13.374 5.393 0    13.9810.018 1.515 0.031 0.036 137 63.862 13.366 5.413 0    13.940 0.019 1.5240.032 0.035 138 63.889 13.339 5.443 0    13.936 0.019 1.511 0.030 0.034139 63.966 13.317 5.416 0    13.920 0.019 1.501 0.031 0.030 140 63.78513.536 5.400 0    13.887 0.017 1.593 0.032 0.029 141 63.605 13.755 5.3850    13.854 0.016 1.684 0.032 0.028 142 63.483 13.863 5.368 0    13.8650.017 1.736 0.032 0.030 143 63.577 13.911 5.335 0    13.767 0.016 1.7580.032 0.031 144 63.420 13.908 5.329 0    13.688 0.017 1.770 0.035 0.032145 63.533 13.952 5.327 0    13.749 0.016 1.776 0.035 0.032 146 63.60613.962 5.327 0    13.701 0.016 1.764 0.032 0.030 147 63.534 13.971 5.3210    13.775 0.016 1.769 0.033 0.031 148 63.497 13.981 5.325 0    13.8060.016 1.773 0.034 0.026 149 63.586 13.935 5.327 0    13.766 0.016 1.7650.036 0.026 150 63.760 13.990 5.018 0    13.801 0.016 1.800 0.040 0.025151 64.329 13.726 4.690 0    13.648 0.130 1.747 0.043 0.025 152 64.97013.353 4.349 0    13.452 0.299 1.708 0.040 0.026 153 65.667 12.945 4.0090    13.242 0.463 1.662 0.035 0.023 154 65.642 12.929 3.999 0    13.1820.516 1.669 0.032 0.027 155 65.761 12.858 3.984 0    13.162 0.520 1.6550.033 0.027 156 65.810 12.813 3.976 0    13.157 0.531 1.650 0.033 0.027157 65.829 12.819 3.959 0.000 13.147 0.535 1.641 0.035 0.027 158 65.85212.778 3.948 0.000 13.172 0.536 1.651 0.036 0.027 159 65.632 12.7224.275 0.000 13.126 0.539 1.639 0.038 0.026 160 65.482 12.643 4.594 0.00013.047 0.538 1.631 0.043 0.027 161 65.466 12.564 4.906 0.674 12.2570.531 1.616 0.045 0.026 162 65.913 12.426 5.228 1.344 11.060 0.520 1.6300.046 0.026 163 66.291 12.297 5.546 2.108 9.874 0.510 1.616 0.048 0.025164 66.613 12.136 5.844 2.989 8.674 0.500 1.600 0.045 0.025 165 67.43812.081 6.103 3.371 7.370 0.490 1.606 0.045 0.026 166 66.985 11.938 6.2964.355 6.861 0.483 1.590 0.044 0.024 167 66.954 11.921 6.410 4.362 6.8020.481 1.587 0.043 0.023 168 66.924 11.903 6.523 4.369 6.743 0.480 1.5840.043 0.022 169 66.822 11.886 6.636 4.403 6.726 0.480 1.577 0.041 0.022170 66.720 11.868 6.749 4.437 6.709 0.479 1.570 0.040 0.021 TiO₂/ Ex.ZrO₂ TiO₂ Fe₂O₃ MnO CoO Total R₂O—Al₂O₃ R_(x)O—Al₂O₃ Fe₂O₃ 116 0.0000.734 0.505 0 0 100 0.556 2.632 1.452 117 0.000 1.217 0.506 0 0 1000.616 2.193 2.407 118 0.000 1.470 0.506 0 0 100 0.470 1.775 2.905 1190.000 1.079 0.322 0 0 100 0.540 2.473 3.353 120 0.000 0.980 0.503 0 0100 0.630 2.469 1.950 121 0.000 0.882 0.689 0 0 100 0.637 2.362 1.280122 0    0.880 0.520 0 0 100 −0.190 1.380 1.692 123 0.009 1.183 0.519 00 100 0.223 1.809 2.278 124 0.009 1.192 0.525 0 0 100 0.246 1.831 2.271125 0.010 1.218 0.534 0 0 100 0.342 1.925 2.281 126 0.011 1.244 0.543 00 100 0.438 2.019 2.291 127 0.010 1.227 0.538 0 0 100 0.339 1.905 2.282128 0.012 1.242 0.541 0 0 100 0.298 1.876 2.295 129 0.013 1.243 0.543 00 100 0.307 1.844 2.290 130 0.012 1.242 0.545 0 0 100 0.436 1.993 2.277131 0.012 1.242 0.547 0 0 100 0.403 1.956 2.270 132 0.013 1.251 0.548 00 100 0.433 1.988 2.284 133 0.011 1.243 0.547 0 0 100 0.582 2.134 2.272134 0.015 1.252 0.548 0 0 100 0.365 1.911 2.284 135 0.015 1.243 0.546 00 100 0.399 1.948 2.275 136 0.013 1.242 0.546 0 0 100 0.625 2.171 2.275137 0.013 1.233 0.543 0 0 100 0.593 2.150 2.271 138 0.013 1.225 0.542 00 100 0.616 2.157 2.262 139 0.012 1.226 0.544 0 0 100 0.621 2.154 2.255140 0.012 1.142 0.548 0 0 100 0.368 1.993 2.084 141 0.011 1.058 0.552 00 100 0.115 1.832 1.915 142 0.013 1.018 0.557 0 0 100 0.019 1.787 1.829143 0.011 0.983 0.558 0 0 100 −0.128 1.662 1.761 144 0.013 1.210 0.561 00 100 −0.203 1.602 2.157 145 0.011 0.991 0.558 0 0 100 −0.186 1.6251.776 146 0.012 0.974 0.558 0 0 100 −0.245 1.551 1.747 147 0.008 0.9650.558 0 0 100 −0.180 1.622 1.729 148 0.007 0.958 0.559 0 0 100 −0.1591.647 1.713 149 0.007 0.959 0.558 0 0 100 −0.153 1.648 1.717 150 0.0070.962 0.562 0 0 100 −0.173 1.666 1.711 151 0.008 1.046 0.589 0 0 1000.051 1.842 1.777 152 0.009 1.152 0.623 0 0 100 0.398 2.146 1.848 1530.009 1.265 0.661 0 0 100 0.759 2.456 1.913 154 0.011 1.299 0.676 0 0100 0.769 2.471 1.922 155 0.010 1.298 0.673 0 0 100 0.824 2.512 1.928156 0.010 1.299 0.674 0 0 100 0.875 2.558 1.928 157 0.010 1.305 0.673 00 100 0.863 2.538 1.939 158 0.010 1.297 0.673 0 0 100 0.931 2.618 1.928159 0.010 1.301 0.672 0 0 100 0.944 2.621 1.938 160 0.012 1.295 0.669 00 100 0.942 2.616 1.937 161 0.011 1.239 0.647 0 0 100 0.898 2.559 1.914162 0.009 1.162 0.619 0 0 100 0.497 2.173 1.878 163 0.009 1.067 0.590 00 100 0.195 1.860 1.808 164 0.007 0.987 0.561 0 0 100 0.027 1.672 1.759165 0.008 0.907 0.536 0 0 100 −0.850 0.801 1.694 166 0.008 0.875 0.520 00 100 −0.239 1.395 1.682 167 0.008 0.870 0.519 0 0 100 −0.275 1.3561.677 168 0.008 0.865 0.517 0 0 100 −0.310 1.317 1.671 169 0.008 0.8630.517 0 0 100 −0.276 1.342 1.670 170 0.008 0.862 0.516 0 0 100 −0.2431.367 1.669

TABLE X Indent Liquidus Temp (° C.)- Liquidus Temp (° C.)- LiqVisc(kP)-24 LiqVisc (kP)-72 Strain Anneal Soft a P Thres. 24 hrs. 72 hrs.hrs. hrs. Ex. Pt. ° C. Pt. ° C. Pt. ° C. (10⁻⁷/° C.) (g/cm³) β-OH (kgf)Air Int. Pt. Air Int. Pt. Air Int. Pt. Air Int. Pt. 116 553 602 865 75.52.413 985 1000 1000 117 550 601 869 76 2.413 15-20 990 995 990 1782 15851782 118 554 605 883 75.4 2.412 1085 1070 1070 257 344 344 119 555 604861 75.8 2.41  990 995 990 120 552 603 863 77.2 2.414 1000 1000 995 121551 602 859 76.6 2.417 1025 1035 1040 739 597 538 122 509 554 812 60.42.369 1015 1030 1020 320 239 290 123 558 608 879.4 75 2.406 0.496 10401050 1050 568 463 463 124 125 126 2.407 127 128 556 607 2.406 0.471 1291065 1065 1065 330 330 330 130 1050 1050 1055 425 425 384 131 132 1331050 1055 1055 439 396 396 134 557 608 2.406 0.465 1075 1065 1070 295362 327 135 136 2.407 1055 1055 1050 388 388 431 137 138 553 603 867.175.1 2.407 0.476 139 140 1045 1055 1050 497 406 449 141 2.408 1025 10401040 870 625 625 142 143 563 614 2.408 0.458 1060 1065 1060 407 368 407144 1070 1070 1075 326 326 295 145 146 147 148 149 561 613 2.407 0.497150 151 2.409 1065 1060 1060 411 454 454 152 1070 1065 1065 418 462 462153 562 614 889.3 76 2.414 0.424 154 155 2.416 1075 1070 1065 416 459507 156 157 158 563 614 2.415 0.441 159 1075 1070 1060 373 412 503 160161 162 1070 1070 1070 238 238 238 163 1060 1060 1065 222 222 203 164519 567 2.383 0.498 1060 1065 1065 206 188 188 165 166 2.368 167 168 169170 513 561 60.3 2.368 0.554 1055 1065 1045 145 122 174 HTV Ex. A B ToT200 P T16 kP T35 kP T160 kP Indentation Threshold 430 116 117−3.30734265 8945.332233 54.12027364 1649 1245 1193 1105 118 −3.94370948610557.79007 −43.72587969 1647 1252 1200 1110 119 120 121 −3.722237129886.571911 −5.851457092 1636 1241 1190 1102 122 −2.9532076628345.482028 28.31570186 1617 1194 1141 1051 123 −3.998970355 10607.22174−47.53043617 1636 1246 1194 1105 124 125 126 127 128 129 −3.6622903549757.207057 2.219928775 1638 1243 1191 1103 130 −3.996576605 10658.76698−57.44735184 1635 1242 1191 1101 131 132 133 −2.838759569 7941.917342113.6168048 1659 1241 1189 1101 134 −2.735780569 7667.308512 140.6120921663 1245 1194 1106 135 136 −2.93989907 8155.890629 98.77631831 16551240 1189 1100 137 138 139 140 −3.885449585 10279.76775 −27.817736891634 1243 1192 1103 141 −3.164251035 8524.185247 88.64381053 1648 12461194 1107 142 143 −4.025680139 10506.38682 −30.3745192 1630 1246 11961108 144 −3.893817967 10158.71538 −9.860563075 1630 1245 1194 1107 145146 147 148 149 150 151 −4.070974917 10734.94875 −43.47341758 1641 12541203 1114 152 −3.982037548 10674.56709 −41.58276344 1657 1262 1210 1120153 154 155 −3.822080075 10411.01967 −27.74613813 1673 1269 1217 1126156 157 158 159 −3.435473834 9488.852121 21.51967142 1676 1264 1211 1120160 161 162 −3.715779117 10364.57238 −69.94158823 1653 1239 1185 1092163 −3.774518631 10532.60088 −94.74870613 1639 1225 1171 1078 164−3.676116288 10214.74357 −76.20201457 1633 1220 1166 1074 165 166 167168 169 170 −3.673843809 10131.86317 −91.71249262 1604.03264 1194.3892771141.187464 1049.524779 Color L D65 SCE L* Ex. As-made T_(n) 620° C.T_(n) 630° C. T_(n) 640° C. T_(n) 660° C. 675-4 700-4 725-4 750-4 775-4800-4 116 117 1.26 3.53 4.73 23.76 118 0.44 0.62 0.94 1.52 119 120 12120.8 7.27 12.11 15.69 122 123 0.6 13.13 124 0.27 3.42 125 0.57 5.07 1260.34 6.35 127 128 129 130 131 132 133 134 135 136 137 138 139 140 0.367.63 141 0.38 6.59 142 143 0.57 5.6 144 0.23 2.12 145 146 147 148 149150 151 0.2 2.85 152 0.46 1.76 153 154 155 0.3 0.98 156 157 158 159 0.412.66 160 161 0.53 0.34 162 0.14 0.17 0.22 0.205 1.93 163 0.41 0.19 0.20.205 3 164 0.24 0.7 165 166 167 0.27 0.72 0.69 1.51 168 0.38 1.2 0.861.52 169 0.28 0.71 0.67 1.43 170 0.51 0.76 1.13 2.14 3.28 13.82 Color aD65 SCE a* Ex. As-made T_(n) 620° C. T_(n) 630° C. T_(n) 640° C. T_(n)660° C. 675-4 700-4 725-4 750-4 775-4 800-4 116 117 0.15 −0.11 −0.49−1.88 118 0.09 0.05 0.01 0.08 119 120 121 12.86 −0.14 −0.05 −0.4 122 123−0.03 −0.99 124 0.01 −0.14 125 0.03 −0.28 126 0.06 −0.67 127 128 129 130131 132 133 134 135 136 137 138 139 140 −0.01 −0.5 141 −0.06 −0.45 142143 0.01 −0.29 144 −0.01 −0.1 145 146 147 148 149 150 151 0 0.08 152−0.08 −0.15 153 154 155 0 −0.01 156 157 158 159 −0.11 −0.1 160 161 0.350.7 162 0 −0.03 −0.07 −0.05 −0.14 163 −0.05 −0.13 −0.1 −0.04 −0.16 164−0.04 −0.09 165 166 167 −0.03 0 −0.01 −0.08 168 0.04 −0.02 0 −0.15 1690.07 −0.05 −0.02 −0.09 170 −0.1 −0.01 −0.03 3.41 −0.03 −0.69 Color b D65SCE b* Ex. As-made T_(n) 620° C. T_(n) 630° C. T_(n) 640° C. T_(n) 660°C. 675-4 700-4 725-4 750-4 775-4 800-4 116 117 −1.34 −4.65 −5.72 −3.94118 −0.28 −0.63 −1.42 −2.33 119 120 121 25.58 −3.97 −3.45 −3.34 122 123−1.04 −7.5 124 −0.78 −4.28 125 −1.1 −5.9 126 −0.73 −6.25 127 128 129 130131 132 133 134 135 136 137 138 139 140 −0.63 −3.62 141 −0.36 −3.44 142143 −0.36 −2.93 144 −0.43 −2.96 145 146 147 148 149 150 151 −0.18 −2.19152 −0.25 −1.87 153 154 155 −0.29 −1.32 156 157 158 159 −0.31 −2.86 160161 −0.27 −0.03 162 −0.36 −0.36 0.07 −0.1 −2.48 163 −0.42 −0.09 0.02−0.15 −3.05 164 −0.11 −1.02 165 166 167 −0.48 −0.6 −0.72 −0.81 168 −0.32−0.85 −0.93 −0.84 169 −0.45 −0.66 −0.81 −0.85 170 −0.53 −0.78 −0.87 1.03−1.6 −0.47

Accordingly, various modifications, adaptations, and alternatives mayoccur to one skilled in the art without departing from the spirit andscope of this disclosure. It should be understood that all suchmodifications and improvements have been deleted herein for the sake ofconciseness and readability but are properly within the scope of thefollowing claims.

What is claimed is:
 1. A glass-ceramic comprising: greater than 0 wt %and less than about 20 wt % of one or more crystalline phases, and acompressive stress of at least about 200 MPa and a depth of layer of atleast about 15 μm, wherein at least one crystalline phase comprises aplurality of crystallites in the Fe₂O₃—TiO₂—MgO system, and thecrystallites comprise at least one of: MgO in an amount in the rangefrom about 5 mol % to about 50 mol %, and Fe₂O₃ in an amount in therange from about 15 mol % to about 65 mol %.
 2. The glass-ceramic ofclaim 1, wherein the glass ceramic exhibits any one of: an edgestrength, as measured by 4-point bend of at least about 700 MPa, anflexural strength, as measured by ring-on-ring testing, of about 2000 Nor greater, and an flexural strength, as measured by abradedring-on-ring testing, of about 1000 N or greater.
 3. The glass-ceramicof claim 1, wherein the glass ceramic exhibits an edge strength, asmeasured by 4-point bend of at least about 700 MPa.
 4. The glass-ceramicof claim 1, wherein the glass ceramic exhibits an flexural strength, asmeasured by ring-on-ring testing, of about 2000 N or greater.
 5. Theglass-ceramic of claim 1, wherein the glass ceramic exhibits an flexuralstrength, as measured by abraded ring-on-ring testing, of about 1000 Nor greater.
 6. The glass-ceramic of claim 1, wherein the crystallitescomprise MgO in an amount in the range from about 5 mol % to about 50mol %.
 7. The glass-ceramic of claim 1, wherein the crystallitescomprise Fe₂O₃ in an amount in the range from about 15 mol % to about 65mol %.
 8. The glass-ceramic of claim 1, wherein the crystallitescomprise TiO₂ in an amount in the range from about 25 mol % to about 45mol %.
 9. The glass-ceramic of claim 1, wherein the glass-ceramiccomprises a color presented in CIELAB color space coordinates for CIEilluminant D65 determined from reflectance spectra measurements using aspectrophotometer with SCE of the following ranges: L*=from about 14 toabout 30; a*=from about −1 to about +3; and b*=from about −7 to about+3.
 10. The glass-ceramic of claim 1, wherein the plurality ofcrystallites form an area fraction of about 15% or less.
 11. Theglass-ceramic of claim 1, wherein the crystallites comprise at least oneof magnetite, pseudobrookite, or ε-Fe₂O₃.
 12. The glass-ceramic of claim1, wherein the one or more crystalline phases comprises one or moreε-Fe₂O₃ crystallites.
 13. The glass-ceramic of claim 1, wherein the oneor more crystalline phases comprises a solid solution of ε-Fe₂O₃ andMgTiO₃.
 14. The glass-ceramic of claim 1, wherein the one or morecrystalline phases comprises a solid solution of MgO, TiO₂, and Fe₂O₃.15. The glass-ceramic of claim 1, wherein the ratio of TiO₂:Fe₂O₃ is inthe range from about 0.1 to about
 3. 16. The glass-ceramic of claim 1,comprising, on an oxide basis, in mol %: SiO₂ in the range from about 50to about 76; Al₂O₃ in the range from about 4 to about 25; P₂O₅+B₂O₃ inthe range from about 0 to about 14; Fe₂O₃ in the range from about 0.25to about 5; R₂O in the range from about 2 to about 20, wherein R₂Oincludes one or more of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O, Cu₂O, and Ag₂O; oneor more nucleating agents in the range from about 0 to about 5; RO inthe range from about 0 to about 20, wherein RO includes one or more ofMgO, CaO, SrO, BaO, and ZnO; and at least one of the compositionalrelationships of: R₂O-Al₂O₃ in the range from about −2 to about 3; andR₂O+RO-Al₂O₃ in the range from about −2 to about 5, wherein thecrystalline phases comprise a plurality of crystallites in theFe₂O₃—TiO₂—MgO system and having an area fraction of about 10% or less.17. The glass-ceramic of claim 16, wherein the one or more nucleatingagents comprises TiO₂.
 18. The glass-ceramic of claim 16, wherein thecomposition comprises, on an oxide basis, in mol %: SiO₂ in an amount inthe range from about 58 to about 72; Al₂O₃ in an amount in the rangefrom about 8 to about 20; B₂O₃ in an amount in the range from about 0 toabout 12; R₂O in an amount in the range from about 2 to about 20; RO inan amount in the range from about 0 to about 10; SnO₂ in an amount inthe range from about 0 to about 0.5; TiO₂ in an amount in the range fromabout 0.25 to about 5; Fe₂O₃ in an amount in the range from about 0.25to about 5; and at least one of the compositional relationships of:R₂O—Al₂O₃ in the range from about −2 to about 3; and R₂O+RO—Al₂O₃ in therange from about −2 to about
 5. 19. An electronic device comprising theglass-ceramic of claim
 1. 20. A light emitting device comprising adisplay cover, wherein the display cover comprises the glass-ceramic ofclaim
 1. 21. A glass-ceramic comprising: greater than 0 wt % and lessthan about 20 wt % of one or more crystalline phases, and a compressivestress of at least about 200 MPa and a depth of layer of at least about15 μm, wherein at least one crystalline phase comprises a plurality ofcrystallites in the Fe₂O₃—TiO₂—MgO system, and the one or morecrystalline phases comprises a solid solution of MgO, TiO₂, and Fe₂O₃.22. A glass-ceramic comprising: greater than 0 wt % and less than about20 wt % of one or more crystalline phases, and a compressive stress ofat least about 200 MPa and a depth of layer of at least about 15 μm,wherein at least one crystalline phase comprises a plurality ofcrystallites in the Fe₂O₃—TiO₂—MgO system, and the one or morecrystalline phases comprises one or more ε-Fe₂O₃ crystallites.